Light-emitting element

Abstract

An object of the present invention is to provide a light-emitting element with high luminous efficiency by providing a novel fluorene derivative. The present invention provides a fluorene derivative represented by the following general formula (G1): JPEG2026010089000066.jpg69120 (J, k, m, and n are 0 or 1, provided that at least one of J and k is 1.)

Description

[Technical Field]

[0001] This invention relates to fluorene derivatives, light-emitting devices, light-emitting devices, electronic devices, and lighting devices. . [Background technology]

[0002] In recent years, electroluminescence has been used. Research and development of such light-emitting elements is actively underway. The basic configuration of these light-emitting elements is a pair This device has a layer containing a light-emitting substance sandwiched between its electrodes. When a voltage is applied to this device... This allows for obtaining light emission from luminescent materials.

[0003] Because these light-emitting elements are self-illuminating, the pixel visibility is higher compared to liquid crystal displays. Furthermore, it has advantages such as not requiring a backlight, and as a flat panel display element It is considered suitable. Furthermore, such light-emitting elements can be manufactured to be thin and lightweight. This is also a major advantage. Furthermore, its extremely fast response time is another notable feature.

[0004] Furthermore, since these light-emitting elements can be formed in a film-like manner, large-area elements can be formed. By doing so, planar light emission can be easily obtained. This is an advantage over incandescent light bulbs and LEDs. This is a characteristic that is difficult to obtain with point light sources such as D, or line light sources such as fluorescent lamps. It also has high potential as a surface light source that can be applied to lighting and other applications.

[0005] The light-emitting element that utilizes electroluminescence is made of an organic compound that emits light. They can be broadly classified according to whether they are inorganic compounds or not, but some luminescent substances use organic compounds. In the case of an electroluminescent (EL) device, applying a voltage to the light-emitting element generates electrons and holes from a pair of electrodes. Each (hole) is injected into a layer containing a light-emitting organic compound, and an electric current flows. From the excited state, in which both the electrons and holes are generated in a luminescent organic molecule, Light is emitted when carriers (electrons and holes) recombine and return to the ground state.

[0006] Due to this mechanism, such light-emitting devices are called current-excited light-emitting devices. The types of excited states that organic compounds can form include singlet excited states and triplet excited states. This is possible, and the emission from the singlet excited state is called fluorescence, while the emission from the triplet excited state is called phosphorescence. They've found out.

[0007] Furthermore, in addition to the luminescence caused by the recombination of electrically excited carriers as mentioned earlier, these excited carriers Another method involves energy being transferred to other organic compounds, which then become excited and emit light. This is because, in general, in organic EL displays, light-emitting material is dispersed (doped) in the light-emitting layer. This is a device structure. The dispersed material is called the host, and the dispersed material is called the dopant. This is because, at high concentrations, the organic molecules that you want to emit light undergo stacking interactions, resulting in poor luminescence efficiency. In cases where the concentration quenching occurs, this organic molecule is used in the host to resolve the issue. This method improves efficiency by suppressing the stacking of the pusher motor. At this time, excitation is performed by current excitation. The excitation energy is transferred from the host that activated it to the dopant, causing the dopant to emit light. do.

[0008] This excitation energy transfer must be a transfer from a higher excitation energy to a lower energy. This does not occur. Therefore, a host material with a high excited state is desirable.

[0009] Furthermore, although organic EL is composed of multiple layers, a carrier transport layer is provided between the light-emitting layer and the electrodes. This is the general practice. One reason for this is that the excitation energy in the light-emitting layer is transferred to the electrode. One reason is to prevent energy transfer and subsequent extinction. Also, the light-emitting layer is adjacent to The carrier transport layer in contact with it is designed so that the excitation energy of the light-emitting layer does not transfer. The carrier transport layer uses a material with a higher excitation energy than the light-emitting layer (exciton blocking material). desirable.

[0010] Furthermore, in organic EL, a carrier injection layer and a carrier transport layer are provided between the light-emitting layer and the electrode. Another reason is to adjust the carrier injection barrier between adjacent layers. This allows for more efficient recombination in the light-emitting layer.

[0011] Regarding such light-emitting elements, improving their device characteristics involves material-dependent issues. There are many such problems, and efforts are being made to overcome them by improving the device structure and developing new materials (for example, (See Patent Document 1). [Prior art documents] [Patent Documents]

[0012] [Patent Document 1] International Publication No. 08 / 062636 [Overview of the Initiative] [Problems that the invention aims to solve]

[0013] One aspect of the present invention provides novel fluorene derivatives as materials with high hole transport properties. One of the objectives is to apply novel fluorene derivatives to light-emitting devices. , one of the objectives is to provide a light-emitting element with high luminous efficiency. One aspect of the present invention is a light-emitting device, an electronic device, and a lighting device with low driving voltage and low power consumption. , and one of the objectives is to provide a light-emitting device, an electronic device, and a lighting device with low driving voltage and low power consumption. One of the objectives is to provide a light-emitting device, an electronic device, and a lighting device with low driving voltage and low power consumption.

Means for Solving the Problems

[0014] One aspect of the present invention is a fluorene derivative represented by the following general formula (G1).

[0015]

Chemical formula

[0016] Also, in the above configuration, R 1 ~R 8 each independently represents any one of the following structural formulas (R-1) to (R-9). is characterized by being any one of the following structural formulas (R-1) to (R-9).

[0017]

Chemical formula

[0018] Furthermore, in the above configuration, α in general formula (G1) 1 ~α 4 Each of these is independently of the structural formula It is characterized by being one of the structural formulas (α-1) to (α-3).

[0019] [ka]

[0020] Furthermore, in the above configuration, Ar in general formula (G1) 1 Ar 2 Each of them is independent of the structure It is one of the formulas (Ar-1) to (Ar-6), and Ar 3 is a structural formula It is characterized by being one of the structural formulas (Ar3-1) to (Ar3-8).

[0021] [ka]

[0022] [ka]

[0023] Furthermore, one aspect of the present invention is represented by the following structural formulas (101), (151), and (118). It is characterized by being one of the following.

[0024] [ka]

[0025] [ka]

[0026] [ka]

[0027] Furthermore, one aspect of the present invention is a light-emitting element having an EL layer between a pair of electrodes, wherein the EL layer is The device comprises at least an emissive layer and a hole transport layer, wherein the hole transport layer contains the fluorene derivative described above. It is characterized by containing.

[0028] Furthermore, one aspect of the present invention is characterized by being formed using the light-emitting element described above. It is a light-emitting device. Furthermore, it is an electric device formed using the light-emitting device described above. It is a sub-device. Furthermore, it is a lighting device formed using the light-emitting device described above.

[0029] Furthermore, one embodiment of the light-emitting device of the present invention comprises the above-mentioned light-emitting element and a control that controls the light emission of the light-emitting element. It has means. In this specification, the light-emitting device refers to an image display device, a light-emitting device Includes a chair or light source (including lighting device). Also includes a connector on the panel, e.g., FP C (Flexible printed circuit) or TAB (Tape Automated Bonding) Tape or TCP (Tape Carrier) A module with a package attached, a TAB tape, or TCP to which a printer is located. A module equipped with a circuit board, or a light-emitting element with COG (Chip On Glass) s) All modules with ICs (integrated circuits) directly mounted using this method are also included as light-emitting devices. Let's assume that.

[0030] Furthermore, electronic devices that use one embodiment of the present invention as a display unit are also included within the scope of the present invention. Therefore, one embodiment of the electronic device of the present invention has a display unit, and the display unit is as described above. It is characterized by being equipped with a light-emitting device.

[0031] Furthermore, a lighting device using one embodiment of the light-emitting device of the present invention shall also be included within the scope of the present invention. Therefore, one aspect of the lighting device of the present invention is characterized by comprising the above-described light-emitting device. . [Effects of the Invention]

[0032] The fluorene derivative of the present invention exhibits high hole transport properties and is therefore mainly used in the EL layer of light-emitting devices. It can be used in the hole transport layer that constitutes the present invention. By using it as a transmission layer to form light-emitting elements, it is possible to form light-emitting elements with high luminescence efficiency. can.

[0033] Furthermore, by using this light-emitting element, a light-emitting device with low power consumption and low driving voltage can be created. Electronic devices and lighting devices can be obtained. [Brief explanation of the drawing]

[0034] [Figure 1] A diagram illustrating a light-emitting element. [Figure 2] A diagram illustrating a light-emitting element. [Figure 3] A diagram illustrating a light-emitting element. [Figure 4] A diagram illustrating a light-emitting device. [Figure 5] A diagram illustrating a light-emitting device. [Figure 6] A diagram illustrating electronic devices. [Figure 7] A diagram illustrating electronic devices. [Figure 8] A diagram illustrating a lighting device. [Figure 9] A diagram illustrating a lighting device. [Figure 10] A diagram showing the 1H NMR chart of 4-phenyl-4'-(9-phenylfluoren-9-yl)triphenylamine. [Figure 11] A diagram showing the absorption spectrum of 4-phenyl-4'-(9-phenylfluoren-9-yl)triphenylamine. [Figure 12] A diagram showing the emission spectrum of 4-phenyl-4'-(9-phenylfluoren-9-yl)triphenylamine. [Figure 13] A figure showing the CV measurement results of 4-phenyl-4'-(9-phenylfluoren-9-yl)triphenylamine. [Figure 14] A diagram showing the 1H NMR chart of 4-phenyl-4'-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine. [Figure 15] A diagram showing the absorption spectrum of 4-phenyl-4'-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine. [Figure 16] A diagram showing the emission spectrum of 4-phenyl-4'-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine. [Figure 17] Figure showing the CV measurement results for 4-phenyl-4'-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine. [Figure 18] A diagram illustrating the light-emitting element of the embodiment. [Figure 19] This figure shows the current density-luminance characteristics of comparative light-emitting element 1 and light-emitting element 2. [Figure 20] This figure shows the voltage-luminance characteristics of comparative light-emitting element 1 and light-emitting element 2. [Figure 21] This figure shows the brightness-current efficiency characteristics of comparative light-emitting element 1 and light-emitting element 2. [Figure 22] A diagram showing the current density-luminance characteristics of the light-emitting element 3. [Figure 23] A diagram showing the voltage-luminance characteristics of the light-emitting element 3. [Figure 24] A diagram showing the brightness-current efficiency characteristics of the light-emitting element 3. [Figure 25] This figure shows the results of the reliability test of the light-emitting element 3. [Figure 26] A diagram showing the current density-luminance characteristics of light-emitting elements 4 and 5. [Figure 27] A diagram showing the voltage-luminance characteristics of light-emitting elements 4 and 5. [Figure 28] A diagram showing the brightness-current efficiency characteristics of light-emitting elements 4 and 5. [Figure 29] This figure shows the results of the reliability tests for light-emitting elements 4 and 5. [Figure 30] This figure shows the current density-luminance characteristics of light-emitting element 6 and comparative light-emitting element 7. [Figure 31] A figure showing the voltage-luminance characteristics of light-emitting element 6 and comparative light-emitting element 7. [Figure 32] This figure shows the brightness-current efficiency characteristics of the light-emitting element 6 and the comparative light-emitting element 7. [Figure 33] A figure showing the emission spectra of light-emitting element 6 and comparative light-emitting element 7. [Figure 34] A diagram showing the current density-luminance characteristics of light-emitting elements 8 to 10. [Figure 35] A diagram showing the voltage-luminance characteristics of light-emitting elements 8 to 10. [Figure 36] This figure shows the brightness-current efficiency characteristics of light-emitting elements 8 to 10. [Figure 37] This figure shows the results of the reliability test for light-emitting elements 8 to 10. [Figure 38] A figure showing the current density-luminance characteristics of the light-emitting element 11 and the comparative light-emitting element 12. [Figure 39] A figure showing the voltage-luminance characteristics of the light-emitting element 11 and the comparative light-emitting element 12. [Figure 40] A figure showing the brightness-current efficiency characteristics of the light-emitting element 11 and the comparative light-emitting element 12. [Figure 41] A figure showing the emission spectra of the light-emitting element 11 and the comparative light-emitting element 12. [Figure 42] A diagram showing the current density-luminance characteristics of the light-emitting element 13. [Figure 43] A diagram showing the voltage-luminance characteristics of the light-emitting element 13. [Figure 44] A diagram showing the brightness-current efficiency characteristics of the light-emitting element 13. [Figure 45]A diagram showing the 1H NMR chart of 4-phenyl-3'-(9-phenylfluoren-9-yl)triphenylamine. [Figure 46] A diagram showing the absorption spectrum of 4-phenyl-3'-(9-phenylfluoren-9-yl)triphenylamine. [Figure 47] A diagram showing the emission spectrum of 4-phenyl-3'-(9-phenylfluoren-9-yl)triphenylamine. [Figure 48] A figure showing the current density-luminance characteristics of the light-emitting element 14 and the comparative light-emitting element 15. [Figure 49] A figure showing the voltage-luminance characteristics of the light-emitting element 14 and the comparative light-emitting element 15. [Figure 50] This figure shows the brightness-current efficiency characteristics of the light-emitting element 14 and the comparative light-emitting element 15. [Modes for carrying out the invention]

[0035] The embodiments of the present invention will be described in detail below with reference to the drawings. However, the present invention is as follows The description is not limited to the present invention, and the form and details may not depart from the spirit and scope of the present invention. Those skilled in the art will readily understand that the parameters can be modified in various ways. Accordingly, the present invention is described below. This should not be interpreted as being limited to the contents described in the embodiment.

[0036] (Embodiment 1) This embodiment describes a fluorene derivative, which is one aspect of the present invention.

[0037] One embodiment of the present invention is a fluorene derivative represented by the general formula (G1). It is the body.

[0038] [ka]

[0039] (In the formula, R 1 ~R8 These are, independently, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and substitutions. It represents either an unsubstituted phenyl group or a substituted or unsubstituted biphenyl group. , α 1 ~α 4 Each of these independently comprises a substituted or unsubstituted arylene group having 6 to 12 carbon atoms. It represents a difference. Also, Ar 1 Ar 2 Each of these independently has 6 to 1 carbon atoms forming the ring. Represents any of the three aryl groups, Ar 3 This is an alkyl group having 1 to 6 carbon atoms, or a substituted or represents an unsubstituted aryl group with 6 to 12 carbon atoms. J, k, m, and n are each independently 0. (The value of k is 1, provided that at least one of J and k is 1.)

[0040] Note, R 1 ~R 8 , α 1 ~α 4 Ar 1 Ar 2 Ar 3 If it has substituents, Examples of substitution groups include methyl, ethyl, propyl, pentyl, and hexyl groups. Examples include aryl groups such as the carboxyl group, phenyl group, biphenyl group, and naphthyl group. It may have multiple substituents. For example, a methylphenyl group, a dimethylphenyl group, t Examples include ert-butylphenyl group and di-tert-butylphenyl group. The substituents may be linked to each other and form a ring (for example, the biphenyl group may be Ar 1 Ma Ar 2 The fluorenyl group forms a ring with the fluorenyl group to become a 9,9'-spirofluorenyl group. Examples include cyclohexyl groups, in which a hexyl group forms a ring.

[0041] Furthermore, using an alkyl group in general formula (G1) improves solubility in organic solvents. It is thought that this is the case. Therefore, when creating an element using this material in a wet process, the alkyl group Using a certain material makes it easier to fabricate the element, which is preferable.

[0042] In the general formula (G1), R 1 ~R 8 These are hydrogen atoms, methyl groups, ethyl groups, and propyl groups. , alkyl groups such as pentyl groups and hexyl groups, substituted or unsubstituted phenyl groups, substituted or Examples include aryl groups such as unsubstituted biphenyl groups. Specifically, structural formula (R-1 The groups shown in )~(R-9) are examples.

[0043] [ka]

[0044] In the general formula (G1), α 1 ~α 4 Examples include substituted or unsubstituted phenylene groups. Specifically, these include the groups shown in structural formulas (α-1) to (α-3).

[0045] [ka]

[0046] In general formula (G1), Ar 1 Ar 2 is a substituted or unsubstituted phenyl group, substituted or Unsubstituted biphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted fluorenyl group Examples include aryl groups such as substituted or unsubstituted spirofluorenyl groups. Specifically, The groups shown in structural formulas (Ar-1) to (Ar-6) are examples. Below, (Ar-4) is , the biphenyl group is Ar 1or Ar 2 The fluorenyl group forms a ring with the 9,9'-spiron This is the fluorenyl group.

[0047] In this case, if a condensed ring group is used, such as (Ar-2) or (Ar-3), the carrier transport properties This is considered to be an improvement and is preferable. Also, at this time, between these fused ring groups and nitrogen atoms ru α 1 or α 2 When it is 1, the molecular band gap (Bg) can be kept wider, which is preferable. Furthermore, structures that use sigma bonds, such as (Ar-5), are derived from the nitrogen atom. The conjugation does not spread easily, and the Bg and T1 levels are high. Therefore, this material is suitable for shorter wavelength emission. Used as a material for a layer adjacent to the light-emitting layer in an optical element, or as a doping material for the light-emitting layer. It is considered possible and preferable. Also, (Ar-2), (Ar-3), and (Ar-4) When using a rigid condensed ring group with a large molecular weight, the thermophysical properties such as the glass transition temperature (Tg) can be improved. Above, preferable

[0048] [ka]

[0049] In general formula (G1), Ar 3 These are methyl group, ethyl group, propyl group, pentyl group, Alkyl groups such as hexyl groups, substituted or unsubstituted phenyl groups, substituted or unsubstituted bifurcations Examples include aryl groups such as henyl groups. Specifically, structural formula (Ar3-1) ~ structural formula The groups shown in (Ar3-8) are examples.

[0050] [ka]

[0051] Specific examples of fluorene derivatives represented by general formula (G1) include structural formula (100) ~ The fluorene derivatives shown in formula (123) and structural formulas (150) to (173) are listed below. This is possible. However, the present invention is not limited to these.

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] One embodiment of the present invention is a method for synthesizing fluorene derivatives by applying various reactions. This can be achieved. For example, by carrying out the synthesis reaction shown below, the general formula (G1) can be obtained. A fluorene derivative according to one aspect of the present invention can be synthesized. The synthesis methods for various fluorene derivatives are not limited to the following methods.

[0061] <Method 1 for synthesizing fluorene derivatives represented by general formula (G1)> As shown in scheme (A-1), the 1-halogenated biphenyl derivative (a1) is lithio After being converted to a Grineer reagent, it is reacted with a benzoyl derivative (a2) and then deoxygenated. By hydroxylating, an aryl fluorene halogen derivative (a3) ​​is obtained.

[0062] [ka]

[0063] Furthermore, in the scheme (A-1) described above, the aryl compound having a halogen group was activated. Next, it is reacted with a benzoyl derivative to form a phenol derivative, and then an acid is added to remove the hydroxyl group (OH). This allows for the formation of fluorene derivatives.

[0064] Examples of its activation include lithiation reactions with alkyllithium reagents and activated magnesium The reaction of converting Nesium into a Grineer reagent can be used. As for alkyllithium, n -Examples include butyllithium, tert-butyllithium, and methyllithium. Acids and Hydrochloric acid can be used as a solvent. Ethers such as diethyl ether can be used as a solvent. Tetrahydrofuran (THF) can be used, and an anhydrous solvent is used.

[0065] Furthermore, as shown in scheme (A-2), a halogenated arene derivative (a4) and aryl By coupling with the amine derivative (a5), the diarylamine derivative (a6) is obtained. This can be obtained.

[0066] [ka]

[0067] Then, as shown in scheme (A-3), the aryl fluorene halogen derivative (a3 By coupling (a6) with the diarylamine derivative (G1 A fluorene derivative represented by ) is obtained.

[0068] [ka]

[0069] Note that X in the above schemes (A-1) to (A-3) 1 , X 2 This represents a halogen, and is reactive. Based on the height, it preferably represents bromine or iodine, more preferably iodine.

[0070] Furthermore, in schemes (A-2) and (A-3) above, aryl compounds having halogen groups A substance and an aryl compound having an amine (primary arylamine compound, secondary arylamine) Coupling reactions with compounds can occur under various reaction conditions, but one example is in the presence of a base. A synthesis method using a metal catalyst can be applied.

[0071] In schemes (A-2) and (A-3) above, the Hartwig-Buchwald reaction is performed The following describes the cases in which it can be used. As the metal catalyst, a palladium catalyst can be used, and the aforementioned As the radium catalyst, a mixture of a palladium complex and its ligand can be used. Examples of palladium complexes include bis(dibenzylideneacetone)palladium(0) and palladium acetate. Examples include zinc(II). Also, as a ligand, tri(tert-butyl) Sphinges, tri(n-hexyl)phosphines, tricyclohexylphosphines, and 1 Examples include 1-bis(diphenylphosphino)ferrocene (abbreviation: DPPF). In addition, substances that can be used as bases include sodium tert-butoxide, etc. Examples include organic bases and inorganic bases such as potassium carbonate. Furthermore, the above reaction is dissolved It is preferable to carry out the process in liquid, and suitable solvents include toluene, xylene, and benzene. Examples include cinzen, etc. However, the catalyst and its ligand, base, etc. that can be used may be different. The solvents are not limited to these. Furthermore, the reaction is carried out in an inert atmosphere such as nitrogen or argon. It is preferable to do it below.

[0072] The above schemes (A-2) and (A-3) show the case where the Ullmann reaction is used. A copper catalyst can be used as the metal catalyst, such as copper(I) iodide or copper(II) acetate. Examples include potassium carbonate and other substances that can be used as bases. Examples include organic bases. Furthermore, the above reaction is preferably carried out in solution and can be used. As a solvent, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)pyrim Examples include dinon (DMPU), toluene, xylene, benzene, etc. However, the above usage The catalysts, bases, and solvents that can be used are not limited to these. Also, the above reaction is performed with nitrogen It is preferable to carry out the procedure under an inert atmosphere such as argon.

[0073] In the Ullmann reaction, a reaction temperature of 100°C or higher yields a shorter reaction time and higher yield. Since a substance is obtained, it is preferable to use a solvent with a high boiling point, such as DMPU or xylene. Furthermore, a reaction temperature higher than 150°C is even more preferable, therefore, DMPU Use this.

[0074] <Method 2 for synthesizing fluorene derivatives represented by general formula (G1)> Also, for example, as shown in scheme (B-1), halogenated fluorene derivative (a3) By coupling it with the arylamine derivative (a5), fluorenyl diaryl A luamine derivative (b1) is obtained.

[0075] [ka]

[0076] Then, as shown in scheme (B-2), fluorenyldiarylamine derivative (b 1) and the halogenated arene derivative (a4) are coupled to form the above general formula ( A fluorene derivative represented by G1) is obtained.

[0077] [ka]

[0078] Note that X in the above schemes (B-1) and (B-2) 2 , X 3 This represents a halogen, and is reactive. Based on the height, it preferably represents bromine or iodine, more preferably iodine.

[0079] In the schemes (B-1) and (B-2) described above, an aryl compound having a halogen group and , aryl compounds containing amines (primary arylamine compounds, secondary arylamine compounds) Coupling reactions with other substances can occur under various reaction conditions, but one example is in the presence of a base. Synthesis methods using metal catalysts can be applied.

[0080] Furthermore, in schemes (B-1) and (B-2), schemes (A-2) and (A-3 Similarly, the Hartwig-Buchwald reaction and the Ullmann reaction can be used.

[0081] <Method 3 for synthesizing fluorene derivatives represented by general formula (G1)> For example, as shown in scheme (C-1), aryl fluorene halogenated derivatives (c1) is lithiated or converted into a Grineer reagent, and then reacted with an organoboronic acid. This yields a fluorenylarylboronic acid derivative (c2) (where J represents 1).

[0082] [ka]

[0083] Furthermore, as shown in scheme (C-2), the triarylamine derivative (c3) is halogenated By performing this compounding process, a halogenated triarylamine derivative (C4) is obtained.

[0084] [ka]

[0085] Then, as shown in scheme (C-3), fluorenylarylboronic acid derivative (c 2) By coupling with a halogenated triarylamine derivative (c4), A fluorene derivative represented by the general formula (G1) is obtained.

[0086] [ka]

[0087] Note that in schemes (C-2) and (C-3), k represents 1.

[0088] Note that X in the above schemes (C-1) to (C-3) 4 , X 5 This represents a halogen, and is reactive. Based on the height, it preferably represents bromine or iodine, more preferably iodine.

[0089] Furthermore, in the scheme (C-1) above, the aryl compound having a halogen group is replaced with a boronic acid group. There are various conditions for the reaction to form an aryl compound having (or an organoboron group). Keem Middle R 1 ~R 8 This indicates hydrogen or an alkyl group.

[0090] One example is lithiation with an alkyllithium reagent followed by the addition of a boron reagent to produce boro It can be oxidized or organoboronized. Examples of alkyllithium reagents include n-butyl Trimethyllithium, methyllithium, etc. can be used as boron reagents. Diethyl ether can be used as a solvent. Any ether or tetrahydrofuran (THF) can be used, and an anhydrous solvent is used. Furthermore, instead of the lithiated reagent, activated magnesium was used to create a Grineer reagent, and this was used It is possible to stay there.

[0091] Furthermore, in the scheme (C-2) described above, there are various reaction conditions for the halogenation reaction, but polar solvent A reaction using a halogenating agent under a medium can be used. The halogenating agent is N - Bromosuccinimide (NBS) and N-iodosuccinimide (NIS), bromine, iodine Potassium iodide, etc., can be used. If bromide is used as a halogenating agent, It is preferable because it can be synthesized inexpensively. Also, when iodide is used as a halogenating agent, the resulting When the reaction using the target substance as a raw material is carried out next (the iodine-substituted portion is more active) Therefore, it is preferable because the reaction proceeds more easily. Note that in scheme (C-2), k represents 1. Halogenation occurs specifically at the para position relative to the amine.

[0092] Furthermore, in the scheme (C-3) above, the aryl compound having a halogen group and the boronic acid The coupling reaction with aryl compounds (arylboronic acids) can occur under various reaction conditions. However, as one example, a synthesis method using a metal catalyst in the presence of a base can be applied. ru.

[0093] The case where the Suzuki-Miyaura reaction is used in the above scheme (C-3) is shown. A palladium catalyst can be used as the catalyst, and the palladium catalyst is palladium A mixture of the complex and its ligand can be used. As the palladium complex, palladium acetate Radium(II), tetrakis(triphenylphosphine), palladium(0), bis(t Examples include palladium(II) dichloride (riphenylphosphine). Also, the coordination As for offspring, tri(ortho-tril)phosphine, triphenylphosphine, and trisyl Examples include chlorohexylphosphine. Also, substances that can be used as the base include... For example, organic bases such as sodium tert-butoxide and inorganic bases such as potassium carbonate. Examples include the following. Furthermore, the reaction is preferably carried out in solution, and the solvents that can be used are also listed. Examples include a mixed solvent of toluene and water, and a mixed solvent of toluene and alcohols such as ethanol and water. A medium, a mixed solvent of xylene and water, a mixed solvent of xylene, an alcohol such as ethanol and water, A mixed solvent of benzene and water, a mixed solvent of benzene and alcohols such as ethanol and water, ethylene Examples include mixed solvents of ethers such as glycol dimethyl ether and water. However, the previous The catalysts, bases, and solvents that can be used are not limited to those listed above. In the field, instead of arylboronic acid, organoboron compounds of aryl derivatives, and Using reel aluminum, aryl zirconium, aryl zinc, aryl tin compounds, etc. It is acceptable to have them present. Furthermore, it is preferable to carry out the above reaction under an inert atmosphere such as nitrogen or argon.

[0094] (Embodiment 2) In this embodiment, the fluorene derivative, which is one aspect of the present invention as described in Embodiment 1, is used. This section describes a light-emitting element formed using a hole transport layer.

[0095] In this embodiment, the light-emitting element has a first electrode that functions as an anode and a cathode that functions as a cathode. It consists of a second electrode and an EL layer provided between the first electrode and the second electrode. In this embodiment, the first electrode of the light-emitting element is more electrically charged than the second electrode. The system is designed so that light is emitted when a voltage is applied to each component in such a way that the position increases.

[0096] Furthermore, the EL layer of the light-emitting element in this embodiment is formed from the first electrode side to the first layer (hole note (Inlet layer), second layer (hole transport layer), third layer (light-emitting layer), fourth layer (electron transport layer), fifth layer The structure includes a layer (electron injection layer).

[0097] The structure of the light-emitting element in this embodiment will be explained with reference to Figure 1. The substrate 101 is a light-emitting element. It is used as a support for an element. As the substrate 101, for example, glass, quartz, plastic, etc. can be used. etc.

[0098] Note that the above substrate 101 may be left in a light-emitting device or an electronic device, which is a product using the light-emitting element according to one aspect of the present invention. However, it may not be left in the final product and may only have the function as a support in the manufacturing process of the light-emitting element. Although it may be left in the light-emitting device or electronic device that is a product using the light-emitting element according to one aspect of the present invention, it may not be left in the final product and may only have the function as a support in the manufacturing process of the light-emitting element.

[0099] For the first electrode 102 formed on the substrate 101, it is preferable to use a metal, alloy, electrically conductive compound, and mixtures thereof having a large work function (specifically, 4.0 eV or more). Specifically, for example, indium tin oxide (ITO: Indium Tin Oxide), indium tin oxide containing silicon or silicon oxide, indium zinc oxide (IZO: Indium Zinc Oxide), indium oxide containing tungsten oxide and zinc oxide, etc. can be mentioned. In addition, gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), titanium (Ti), or nitrides of metal materials (for example, titanium nitride), etc. can be mentioned. However, in the present invention, since the first layer 111 of the EL layer 103 formed in contact with the first electrode 102 is formed using a composite material that facilitates hole injection regardless of the work function of the first electrode 102, any known material can be used as long as it is a material possible as an electrode material (for example, metals, alloys, electrically conductive compounds, and mixtures thereof, and also including elements belonging to Group 1 or Group 2 of the periodic table). In the present invention, since the first layer 111 of the EL layer 103 formed in contact with the first electrode 102 is formed using a composite material that facilitates hole injection regardless of the work function of the first electrode 102, any known material can be used as long as it is a material possible as an electrode material (for example, metals, alloys, electrically conductive compounds, and mixtures thereof, and also including elements belonging to Group 1 or Group 2 of the periodic table).

[0100] These materials are typically deposited by sputtering. For example, indium oxide Zinc oxide (IZO) is a target compound made by adding 1-20 wt% zinc oxide to indium oxide. Indium oxide containing tungsten oxide and zinc oxide is indium oxide. In contrast, the target contains 0.5-5 wt% tungsten oxide and 0.1-1 wt% zinc oxide. By using a tweezers, it can be formed by sputtering. In addition, vacuum deposition is also possible. They may be manufactured by methods such as coating, inkjet, or spin coating.

[0101] Furthermore, among the EL layer 103 formed on the first electrode 102, the one in contact with the first electrode 102 In the case where a layer containing a composite material, described later, is used as the material for the first layer 111 formed by the process, In addition, the material used for the first electrode 102 can be various metals, regardless of the magnitude of the work function. Gold, electrically conductive compounds, and mixtures thereof can be used. For example, aluminum Aluminum (Al), silver (Ag), and aluminum-containing alloys (AlSi) can also be used. can.

[0102] Furthermore, elements belonging to Group 1 or Group 2 of the periodic table, which are materials with a small work function, That is, alkali metals such as lithium (Li) and cesium (Cs), and magnesium (Mg) , alkaline earth metals such as calcium (Ca) and strontium (Sr), and compounds containing these. Rare earth elements such as gold (MgAg, AlLi), europium (Eu), and ytterbium (Yb) Metals and alloys containing them can also be used.

[0103] Furthermore, alkali metals, alkaline earth metals, and alloys containing these are used for the first electrode. When forming 102, a vacuum evaporation method or a sputtering method can be used. Further more, when using a silver paste or the like, a coating method, an inkjet method, or the like can be used.

[0104] For the EL layer 103 formed on the first electrode 102, known materials can be used, and either a low molecular weight compound or a high molecular weight compound can be used. Note that the material for forming the EL layer 10 3 includes not only those composed only of organic compounds but also those including a part of inorganic compounds.

[0105] The EL layer 103 is formed by appropriately combining and laminating a hole injection layer containing a substance with high hole injection property, a hole transport layer containing a substance with high hole transport property, a light emitting layer composed of a light emitting substance, an electron transport layer containing a substance with high electron transport

[0106] property, an electron injection layer containing a substance with high electron injection property, and the like. Note that the EL layer 103 shown in Fig. 1(A) is laminated in the order of the first layer (hole injection layer) 111, the second layer (hole transport layer) 112, the third layer (light emitting layer) 113, the fourth layer (electron

[0107] transport layer) 114, and the fifth layer (electron injection layer) 115 from the side of the first electrode 102. The first layer 111, which is a hole injection layer, is a hole injection layer containing a substance with high hole injection property. Examples of the substance with high hole injection property include molybdenum oxide, titanium oxide, vanadium oxide,This can be done. In addition, as low molecular weight organic compounds, phthalocyanine (abbreviation: H2Pc), Copper(II) phthalocyanine (abbreviation: CuPc), vanadylphthalocyanine (abbreviation: VOP) Examples include phthalocyanine compounds such as those in c). The present invention as shown in Embodiment 1 is also relevant. A fluorene derivative, which is one embodiment of the invention, can also be used in the same manner.

[0108] Furthermore, the low molecular weight organic compound 4,4',4''-tris(N,N-diphenylamine) (N) Triphenylamine (abbreviation: TDATA), 4,4',4''-Tris[N-(3- Methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), 4,4'-Bis[N-(4-diphenylaminophenyl)-N-phenylamino]bife Nyl (abbreviation: DPAB), 4,4'-bis(N-{4-[N'-(3-methylphenyl) -N'-phenylamino]phenyl}-N-phenylamino)biphenyl (abbreviation: DNT) PD), 1,3,5-Tris[N-(4-diphenylaminophenyl)-N-phenyl [Mino]benzene (abbreviation: DPA3B), 3-[N-(9-phenylcarbazole-3-I [Phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA1), 3 ,6-bis[N-(9-phenylcarbazole-3-yl)-N-phenylamino]-9 -Phenylcarbazole (abbreviation: PCzPCA2), 3-[N-(1-naphthyl)-N- (9-phenylcarbazole-3-yl)amino]-9-phenylcarbazole (abbreviation: Aromatic amine compounds such as PCzPCN1 can also be mentioned. A fluorene derivative, which is one embodiment of the present invention, can also be used in the same manner.

[0109] Furthermore, polymer compounds (oligomers, dendrimers, polymers, etc.) can also be used. For example, poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyl carboxylazole) Phenylamine (abbreviation: PVTPA), poly[N-(4-{N'-[4-(4-diphenylamine) [Nylamino)phenyl]phenyl-N'-phenylamino}phenyl)methacrylamide ](Abbreviation: PTPDMA) Poly[N,N'-bis(4-butylphenyl)-N,N'-bi Examples of high-molecular-weight compounds include poly(phenyl)benzidine (abbreviated as Poly-TPD). Also, poly(3,4-ethylenedioxythiophene) / poly(styrenesulfonic acid) (PEDOT / PSS), Polyaniline / Poly(styrene sulfonate) (PAni / PS Polymer compounds to which acids such as S) have been added can also be used.

[0110] Furthermore, the first layer 111 contains an acceptor substance in a material with high hole transport properties. A composite material can be used. Furthermore, an acceptor material can be added to a material with high hole transport properties. By using a material containing this substance, the material used to form the electrodes can be selected regardless of the work function of the electrodes. This is possible. In other words, not only materials with a large work function as the first electrode 102, but also work Materials with small function can be used. These composite materials are materials with high hole transport properties. It can be formed by co-depositing with an acceptor material. In this context, "composite" refers not only to mixing two materials, but also to mixing multiple materials. This refers to a state in which electric charge can be transferred between materials.

[0111] Organic compounds used in composite materials include aromatic amine compounds, carbazole derivatives, and aromatic compounds. Various chemical compounds such as aromatic hydrocarbons and polymer compounds (oligomers, dendrimers, polymers, etc.) Compounds can be used. Furthermore, as organic compounds used in composite materials, hole transport properties are... It is preferable that it is a highly organic compound. Specifically, 10 -6 cm 2 Hole transition of / Vs or greater It is preferable that the material has mobility. However, it is preferable that the material has higher hole transport than electron transport. If so, other materials may be used. Below are organic materials that can be used in composite materials. List the compounds specifically.

[0112] Examples of organic compounds that can be used in composite materials include MTDATA and TDAT. A, DPAB, DNTPD, DPA3B, PCzPCA1, PCzPCA2, PCzPC N1,4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation) :NPB or α-NPD), N,N'-bis(3-methylphenyl)-N,N'-diph Aromatic compounds such as phenyl-[1,1'-biphenyl]-4,4'-diamine (abbreviation: TPD) Min compounds, 4,4'-di(N-carbazolyl)biphenyl (abbreviated as CBP), 1,3 ,5-Tris[4-(N-carbazolyl)phenyl]benzene (abbreviation: TCPB), 9- [4-(N-carbazolyl)]phenyl-10-phenylanthracene (abbreviation: CzPA) ), 1,4-bis[4-(N-carbazolyl)phenyl]-2,3,5,6-tetraphenyl Examples of carbazole derivatives include ylbenzene. A fluorene derivative, which is one embodiment of the present invention, can also be used in the composite material.

[0113] Also, 2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t -BuDNA), 2-tert-butyl-9,10-di(1-naphthyl)anthracene, 9,10-Bis(3,5-diphenylphenyl)anthracene (abbreviation: DPPA), 2- tert-butyl-9,10-bis(4-phenylphenyl)anthracene (abbreviation: t- BuDBA), 9,10-di(2-naphthyl)anthracene (abbreviation: DNA), 9,10 -Diphenylanthracene (abbreviation: DPaNth), 2-tert-butylanthracene (Abbreviation: t-BuAnth), 9,10-bis(4-methyl-1-naphthyl)anthrace 9,10-bis[2-(1-naphthyl)phenyl]-2-ter t-butyl-anthracene, 9,10-bis[2-(1-naphthyl)phenyl]anthracene Sen, 2,3,6,7-tetramethyl-9,10-di(1-naphthyl)anthracene, etc. Aromatic hydrocarbon compounds can be cited as examples.

[0114] Furthermore, 2,3,6,7-tetramethyl-9,10-di(2-naphthyl)anthracene ,9,9'-biantryl,10,10'-diphenyl-9,9'-biantryl,10 ,10'-bis(2-phenylphenyl)-9,9'-biantryl, 10,10'-bi Su[(2,3,4,5,6-pentaphenyl)phenyl]-9,9'-biantryl, A Ntracene, tetracene, rubrene, perylene, 2,5,8,11-tetra(tert- Butyl perylene, pentacene, coronene, 4,4'-bis(2,2-diphenylvinyl) ) Biphenyl (abbreviation: DPVBi), 9,10-bis[4-(2,2-diphenylvinyl) Aromatic hydrocarbon compounds such as phenyl]anthracene (abbreviation: DPVPA) should also be mentioned. It is possible.

[0115] Furthermore, as an acceptor substance, 7,7,8,8-tetracyano-2,3,5,6 -Organic compounds such as tetrafluoroquinodimethane (abbreviation: F4-TCNQ), chloranil, and Examples include transition metal oxides. Also, in groups 4 to 8 of the periodic table... We can list the oxides of the metals to which they belong. Specifically, vanadium oxide, niobium oxide, Tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, ray oxide Tium is preferred because of its high electron-accepting ability. In particular, molybdenum oxide is stable even in the atmosphere. Therefore, it is preferable because it has low hygroscopicity and is easy to handle.

[0116] Furthermore, the polymer compounds mentioned above, such as PVK, PVTPA, PTPDMA, and Poly-TPD... A composite material is formed using the material and the acceptor material described above, and used in the first layer 111. The fluorene derivative, which is one aspect of the present invention as shown in Embodiment 1, is also described above. A composite material can be formed by combining it with an acceptor material and used in the first layer 111. Cut.

[0117] The second layer 112, which is a hole transport layer, is a layer containing a substance with high hole transport properties. The second layer 112 in the embodiment is one aspect of the present invention as described in Embodiment 1. A fluorene derivative will be used. The fluorene derivative in one aspect of the present invention described above is Because it has a wide band gap, the second layer 112 formed with this fluorene derivative is It is difficult to absorb the exciton energy generated in the adjacent third layer 113 (light-emitting layer), and the excitons It can be efficiently confined within the light-emitting layer. Therefore, a highly efficient light-emitting element can be obtained.

[0118] Furthermore, both the first layer 111 and the second layer 112 contain the first of the present invention as described in Embodiment 1. A fluorene derivative can also be used. In this case, the fabrication of the device becomes simpler. This improves material utilization efficiency. Also, the first layer 111 and the second layer 112 Because the energy diagrams will be the same or similar, the first layer 111 and the second layer 112 This makes it easier for carriers to move between them.

[0119] The third layer 113 is an emissive layer containing a highly luminescent material. The listed low-molecular-weight organic compounds can be used. One embodiment, a fluorene derivative, also exhibits luminescence and can be used as a luminescent material.

[0120] Examples of luminescent materials include fluorescent compounds that emit fluorescence and phosphorescent compounds that emit phosphorescence. You can use it.

[0121] Examples of fluorescent materials that can be used in the light-emitting layer 113 include blue light-emitting materials. As N,N'-bis[4-(9H-carbazol-9-yl)phenyl]-N,N' -Diphenylstilbene-4,4'-diamine (abbreviation: YGA2S), 4-(9H-Cal Bazole-9-yl)-4'-(10-phenyl-9-anthryl)triphenylamine Examples include (abbreviated as YGAPA).

[0122] As for green light-emitting substances, N-(9,10-diphenyl-2-anthryl)-N,9 -Diphenyl-9H-carbazole-3-amine (abbreviation: 2PCAPA), N-[9,1 0-Bis(1,1'-biphenyl-2-yl)-2-anthryl]-N,9-diphenyl -9H-carbazole-3-amine (abbreviation: 2PCABPhA), N-(9,10-diph (phenyl-2-anthryl)-N,N',N'-triphenyl-1,4-phenylenediamine N (abbreviation: 2DPAPA), N-[9,10-bis(1,1'-biphenyl-2-yl) -2-anthryl]-N,N',N'-triphenyl-1,4-phenylenediamine (abbreviated) Name: 2DPABPhA), 9,10-bis(1,1'-biphenyl-2-yl)-N-[ 4-(9H-carbazole-9-yl)phenyl]-N-phenylanthracene-2-a Min (abbreviation: 2YGABPhA), N,N,9-triphenylanthracene-9-amine Examples include (abbreviated as DPhAPhA).

[0123] Examples of yellow-colored luminescent substances include rubrene and 5,12-bis(1,1'-biphenyl-4- Examples include yl-6,11-diphenyltetracene (abbreviated as BPT). Furthermore, As a red-colored luminescent substance, N,N,N',N'-tetrakis(4-methylphenyl)te Spiral-5,11-diamine (abbreviation: p-mPhTD), 7,14-diphenyl-N,N ,N',N'-tetrakis(4-methylphenyl)acenaphtho[1,2-a]fluorane Examples include ten-3,10-diamine (abbreviated as p-mPhAFD).

[0124] Furthermore, examples of phosphorescent compounds that can be used in the light-emitting layer 113 include blue-colored phosphorescent compounds. As a photomaterial, bis[2-(4',6'-difluorophenyl)pyridinate-N,C 2’ Iridium(III) tetrakis(1-pyrazolyl) borate (abbreviation: Fir6), S[2-(4',6'-difluorophenyl)pyridinate-N,C 2’ Iridium (I II) Picolinate (abbreviation: Firpic), Bis{2-[3',5'-Bis(Triful Oromethyl)phenyl]pyridinate-N,C 2’ Iridium(III) picolinate Abbreviation: Ir(CF3ppy)2(pic)), bis[2-(4',6'-difluorophen Nyl)pyridinate-N,C 2’ Iridium(III) acetylacetonate (abbreviation: F Examples include Ir(acac)). Also, as a green light-emitting material, there is tris(2-f Enylpyridinate-N,C 2’ Iridium(III) (abbreviation: Ir(ppy)3), S(2-phenylpyridinato-N,C) 2’ Iridium(III) acetylacetonate (Abbreviation: Ir(ppy)2(acac)), bis(1,2-diphenyl-1H-benzoyl) Midazolato) Iridium(III) acetylacetonate (abbreviation: Ir(pbi)2(a CAC)), Bis(benzo[H]quinolinate)iridium(III) acetylacetonate Examples include Ir(bzq)2(acac) and others. Also, yellow-colored light-emitting materials. As such, bis(2,4-diphenyl-1,3-oxazolato-N,C 2’ )iridium( III) Acetylacetonate (abbreviation: Ir(dpo)2(acac)), bis[2-( 4'-Perfluorophenylphenyl)pyridinate]iridium(III)acetylacetate Tonat (abbreviation: Ir(p-PF-ph)2(acac)), bis(2-phenylbenzo) Thiazolato-N,C 2’ Iridium(III) acetylacetonate (abbreviation: Ir(b) Examples include tris(2-)(acac). Also, as an orange-colored luminescent material, tris(2-) Phenylquinolinate-N,C 2’Iridium(III) (abbreviation: Ir(pq)3), S(2-phenylquinolinato-N,C) 2’ Iridium(III) acetylacetonate Examples include (abbreviation: Ir(pq)2(acac)). Also, as a red light-emitting material... bis[2-(2'-benzo[4,5-α]thienyl)pyridinate-N,C 3’ ] Iri Dium(III) acetylacetonate (abbreviation: Ir(btp)2(acac)), bis (1-Phenylisoquinolinato-N,C 2’ Iridium(III) Acetylaceton (Abbreviation: Ir(piq)2(acac)), (acetylacetonato)bis[2,3-bi [S(4-fluorophenyl)quinoxalinato] Iridium(III) (abbreviation: Ir(Fd) pq)2(acac)), 2,3,7,8,12,13,17,18-Octaethyl-2 Examples include organometallic complexes such as 1H,23H-porphyrin platinum(II) (abbreviated as PtOEP). It can be done. Also, tris(acetylacetonate)(monophenanthroline)terbium(I II) (Abbreviation: Tb(acac)3(Phen)), Tris(1,3-diphenyl-1, 3-Propanedionato)(monophenanthroline) europium(III) (abbreviation: Eu (DBM)3(Phen)), Tris[1-(2-Tenoyl)-3,3,3-Trifluo [Roacetonate](monophenanthroline) europium(III) (abbreviation: Eu(TTA) Rare earth metal complexes such as 3(Phen) emit light from rare earth metal ions (different multiplicities). Because it involves an electronic transition, it can be used as a phosphorescent compound.

[0125] Furthermore, the third layer 113 is configured to disperse the aforementioned highly luminescent material in other materials. It is also acceptable. Furthermore, when dispersing, the concentration of the substance to be dispersed (dopant) should be the mass ratio. It is preferable to keep the total amount below 20%. Also, the material used to disperse the luminescent substance. As for the host, any known substance can be used, but a luminescent substance (dopant) The lowest unoccupied orbital level (LUMO level) is shallower (smaller absolute value) than the highest occupied orbital level It is preferable to use a substance with a deep HOMO level (large absolute value). The band gap (Bg: the difference between the HOMO level and the LUMO level) of the luminescent dopant is B It is preferable that it is greater than g. Also, if the dopant's emission is fluorescent, the S1 level is phosphorus. In the case of photodynamic therapy, it is preferable that the T1 level is higher in the host than in the dopant.

[0126] Specifically, tris(8-quinolinolato)aluminum(III) (abbreviation: Alq), Tris(4-methyl-8-quinolinolato)aluminum(III) (abbreviation: Almq3) , bis(10-hydroxybenzo[h]quinolinato)beryllium(II) (abbreviation: BeB q2), bis(2-methyl-8-quinolinolate)(4-phenylphenolate)aluminium Mu(III) (abbreviation: BAlq), bis(8-quinolinolato)zinc(II) (abbreviation: Zn) q) Bis[2-(2-benzoxazolyl)phenolate]zinc(II) (abbreviation: ZnP) BO), bis[2-(2-benzothiazolyl)phenolate]zinc(II) (abbreviation: ZnB) Metal complexes such as TZ can be used.

[0127] Also, 2-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-1, 3,4-Oxadiazole (abbreviation: PBD), 1,3-Bis[5-(p-tert-buty [Oxadiazole-2-yl]benzene (abbreviation: OXD-7) ), 3-(biphenyl-4-yl)-4-phenyl-5-(4-tert-butylphenyl (Lu)-1,2,4-triazole (abbreviation: TAZ), 2,2',2''-(1,3,5- Benzenetriyl)tris(1-phenyl-1H-benzoimidazole) (abbreviation: TPB) I) Vasophenanthroline (abbreviation: BPhen), Vasocuproin (abbreviation: BCP) Heterocyclic compounds such as the following can be used.

[0128] In addition, 9-[4-(10-phenyl-9-antryl)phenyl]-9H-carbazo CzPA (abbreviation: CzPA), 3,6-diphenyl-9-[4-(10-phenyl-9-an [Tolyl)phenyl]-9H-carbazole (abbreviation: DPCzPA), 9,10-bis(3 ,5-diphenylphenyl)anthracene (abbreviation: DPPA), 9,10-di(2-naph Chill anthracene (abbreviation: DNA), 2-tert-butyl-9,10-di(2-naph Chill anthracene (abbreviation: t-BuDNA), 9,9'-biantril (abbreviation: BAN T), 9,9'-(stilben-3,3'-diyl)diphenanthrene (abbreviation: DPNS) ), 9,9'-(stilbene-4,4'-diyl)diphenanthrene (abbreviation: DPNS2) ), 3,3',3''-(benzene-1,3,5-triyl)tripylene (abbreviation: TPB) 3) Condensed aromatic compounds such as those mentioned above can also be used.

[0129] Furthermore, multiple types of materials can be used to disperse the luminescent substance. For example, Further crystallization-inhibiting substances such as rubrene may be added to suppress crystallization. To more efficiently transfer energy to luminescent materials, NPB or Alq The following may be added. Furthermore, one embodiment of the present invention shown in Embodiment 1 is a fluorene derivative. The human body can also be used. In this way, a configuration in which a highly luminescent substance is dispersed in other substances and This makes it possible to suppress the crystallization of the third layer 113. Furthermore, highly luminescent materials High concentration of quality can suppress concentration quenching.

[0130] Furthermore, among the substances mentioned above, a particularly electron-transporting substance is used to disperse a luminescent substance. It is more preferable to form a third layer 113. Specifically, the metal complex, heterocycle described above. Compounds, including CzPA, DNA, t-BuDNA, and later, A polymer compound can be used as a material for the fourth layer 114 shown in the diagram. It is also possible.

[0131] Furthermore, the following polymer compounds can also be used for the third layer 113.

[0132] As for blue-emitting materials, poly(9,9-dioctylfluorene-2,7-diyl) (Abbreviation: PFO), poly[(9,9-dioctylfluorene-2,7-diyl)-co- (2,5-dimethoxybenzene-1,4-diyl) (abbreviation: PF-DMOP), poly{ (9,9-dioctylfluorene-2,7-diyl)-co-[N,N'-diyl-(p-bu Examples include Tylphenyl-1,4-diaminobenzene (abbreviation: TAB-PFH). It can be done.

[0133] Examples of green light-emitting substances include poly(p-phenylenevinylene) (abbreviation: PPV), poly [(9,9-dihexylfluorene-2,7-diyl)-alt-co-(benzo[2, 1,3] Thiadiazole-4,7-diyl) (abbreviation: PFBT), poly[(9,9-di) Octyl-2,7-divinylenefluorenylene)-alt-co-(2-methoxy-5- Examples include (2-ethylhexyloxy)-1,4-phenylene).

[0134] As for orange to red luminescent substances, poly[2-methoxy-5-(2'-ethylhexoxy [C)-1,4-phenylenevinylene] (abbreviation: MEH-PPV), poly(3-butylthio) Fen-2,5-diyl) (abbreviation: R4-PAT), poly{[9,9-dihexyl-2, 7-Bis(1-cyanovinylene)fluorenylene]-alt-co-[2,5-bis(N ,N'-diphenylamino)-1,4-phenylene]}, poly{[2-methoxy-5-( 2-ethylhexyloxy)-1,4-bis(1-cyanovinylenephenylene)]-alt -co-[2,5-bis(N,N'-diphenylamino)-1,4-phenylene]}(abbreviated) Examples include CN-PPV-DPD.

[0135] The light-emitting layer 113 can also be formed from two or more layers. For example, the first light-emitting layer When the first light-emitting layer and the second light-emitting layer are stacked in order from the hole transport layer side to form the light-emitting layer 113, A material with hole transport properties is used as the host material for the layer, and as the host material for the second light-emitting layer A material having electron transport properties can be used. More preferably, the host material of the first light-emitting layer. The material used is one that has higher hole transport properties than electron transport properties, and the host material of the second light-emitting layer is a hole transport material. A material with higher electron transport properties than electron emitting properties is preferred. With the above configuration, the first light-emitting layer and the The space between the second light-emitting layer and the first light-emitting layer becomes a light-emitting site, resulting in a more efficient device.

[0136] When the light-emitting layer having the above structure is composed of multiple materials, it can be deposited by vacuum deposition. Co-deposition or mixed solution is used by inkjet, spin coating, or dip coating. It can be manufactured using methods such as the T method.

[0137] The fourth layer 114 is an electron transport layer containing a material with high electron transport properties. Examples of low molecular weight organic compounds include Alq, Almq3, BeBq2, BAlq, Metal complexes such as Znq, ZnPBO, and ZnBTZ can be used. Besides bodies, there are also heteroalgebras such as PBD, OXD-7, TAZ, TPBI, BPhen, and BCP. Compounds can be used. The substances mentioned here are mainly 10 -6 cm 2 / Vs or more It is a substance that possesses electron mobility. Furthermore, any substance with higher electron transport capabilities than hole transport is also considered. Other materials may be used as the electron transport layer. Furthermore, the electron transport layer is not limited to a single layer. Furthermore, two or more layers made of the above-mentioned material may be stacked on top of each other.

[0138] A polymer compound can also be used for the fourth layer 114. For example, poly[(9,9- (Dihexylfluorene-2,7-diyl)-co-(pyridine-3,5-diyl)(abbreviated) Name: PF-Py), Poly[(9,9-dioctylfluorene-2,7-diyl)-co- (2,2'-bipyridine-6,6'-diyl) (abbreviation: PF-BPy) etc. It is possible.

[0139] Furthermore, the fifth layer 115 is an electron injection layer containing a material with high electron injection potential. 15 includes lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride ( Alkali metals such as CaF2, alkaline earth metals, or compounds thereof are used. It is possible. Other substances that have electron transport properties include alkali metals, alkaline earth metals, and or substances containing those compounds, specifically those containing magnesium (Mg) in Alq. Materials such as those provided may be used. In this case, electron injection from the second electrode 104 is also possible. This allows for more efficient execution.

[0140] The second electrode 104 is made of a metal or alloy with a small work function (specifically, 3.8 eV or less). Electrically conductive compounds and mixtures thereof can be used. Such cathode materials Specific examples include elements belonging to Group 1 or Group 2 of the periodic table, namely lithium ( Alkali metals such as lithium (Li) and cesium (Cs), as well as magnesium (Mg) and calcium. Alkaline earth metals such as (Ca), strontium (Sr), and alloys containing these (M Rare earth metals such as γAg, AlLi, europium (Eu), and ytterbium (Yb) Examples include alloys containing these materials.

[0141] Furthermore, alkali metals, alkaline earth metals, and alloys containing these are used for the second electrode 104 When forming it, vacuum deposition or sputtering can be used. Also, silver paint When using a stencil or similar material, coating methods or inkjet methods can be used.

[0142] Furthermore, by providing a fifth layer 115, regardless of the magnitude of the work function, Al, Ag, Various conductive materials such as ITO, silicon, or indium oxide-tin oxide containing silicon oxide. The second electrode 104 can be formed using these conductive materials. The film can be formed using methods such as inkjet coating, spin coating, etc.

[0143] Furthermore, the first layer (hole injection layer) 111, the second layer (hole transport layer) 112, and the third layer (hole injection layer) The optical layer (113), the fourth layer (electron transport layer) (114), and the fifth layer (electron injection layer) (115) are arranged in order. The method for producing the EL layer 103, which is formed by subsequent lamination, can be a dry method or a wet method, or various other methods. The following methods can be used: for example, vacuum deposition, inkjet, or spin coating. Methods such as the T method can be used. Furthermore, different film deposition methods may be used for each layer. .

[0144] Regarding the second electrode 104, not only dry methods such as sputtering and vacuum deposition are used, but also It can be formed using a paste of a metallic material by a wet method such as the sol-gel method.

[0145] Furthermore, the first electrode 102, the first layer (hole injection layer) 111, and the second layer (hole transport layer) are respectively... The space between layer 112 and the third layer (luminescent layer) 113 mainly carries holes, so the carriers between adjacent layers A. To reduce the implantation barrier, the HOMO levels (work function in the case of metals) are the same or of similar magnitude. It is desirable to have a third layer (light-emitting layer) 113 and a fourth layer (electron transport layer). The space between layer 114, the fifth layer (electron injection layer) 115, and the second electrode 104 is mainly for electron flow. Therefore, in order to reduce the carrier injection barrier between adjacent layers, the LUMO level (in the case of metals) It is desirable that the function(s) be the same or of similar magnitude. Preferably, the difference should be within 0.2eV. More preferably, it is within 0.1 eV.

[0146] Furthermore, deliberately considering the space between the second layer (hole transport layer) 112 and the third layer (luminescence layer) 113. LOMO between HOMO level, third layer (emission layer) 113, and fourth layer (electron transport layer) 114 By increasing the difference in energy levels, carriers are confined in the light-emitting layer, resulting in a more efficient light-emitting element. This is preferable. However, in this case, if the barrier is too large, the driving voltage will become high, negatively impacting the element. Therefore, the difference is preferably within 0.4 eV, more preferably within 0.2 eV. It is preferable to do so.

[0147] The light-emitting element according to one aspect of the present invention described above has a first electrode 102 and a second electrode 104 The potential difference created between them causes a current to flow, and holes and electrons recombine in the EL layer 103. It emits light as a result of the first electrode 102 or the second electrode 104 It is extracted to the outside through one or both of the following electrodes. Thus, the first electrode 102 or the Either one or both of the two electrodes 104 are translucent electrodes.

[0148] Furthermore, if only the first electrode 102 is a translucent electrode, as shown in Figure 2(A) Thus, the light emitted in the EL layer 103 is extracted from the substrate 101 side through the first electrode 102. This is done. Also, if only the second electrode 104 is a translucent electrode, see Figure 2(B). As shown, the light emitted in the EL layer 103 passes through the second electrode 104 to the side opposite the substrate 101. It is removed from. Furthermore, both the first electrode 102 and the second electrode 104 are light-transmitting. In the case of an electrode having such an electrode, as shown in Figure 2(C), the light emitted in the EL layer 103 is Through electrode 102 and electrode 104, on the substrate 101 side and on the side opposite to substrate 101 It is extracted from both sides.

[0149] The layer provided between the first electrode 102 and the second electrode 104 is as described above. It is not limited to the following. At least a second layer 112 which is a hole transport layer, and a light-emitting layer Any configuration having a third layer 113 is acceptable, other than those described above.

[0150] Furthermore, as shown in Figure 1(B), a second electrode 104 that functions as a cathode is placed on the substrate 101. Alternatively, the structure may be one in which the EL layer 103 and the first electrode 102, which functions as an anode, are sequentially stacked. In this case, the EL layer 103 is the fifth layer 115 and the fourth layer on the second electrode 104. Layers 114, 3rd layer 113, 2nd layer 112, 1st layer 111, and 1st electrode 102 are stacked sequentially. It will have a layered structure.

[0151] Furthermore, by using the light-emitting element of the present invention, a passive matrix type light-emitting device and a thin-film type can be created. Active matrix type LEDs in which the drive of light-emitting elements is controlled by transistors (TFTs). Optical devices can be fabricated.

[0152] Furthermore, the structure of the TFT when fabricating an active matrix type light-emitting device is particularly It is not limited to this. For example, staggered or inverse staggered TFTs can be used as appropriate. Furthermore, the driving circuit formed on the TFT substrate also consists of N-type and P-type TFTs. It may be either an N-type TFT or a P-type TFT consisting of only one of them. This is also acceptable. Furthermore, the crystallinity of the semiconductor film used in the TFT is not particularly limited. Amorphous semiconductor films may be used, or crystalline semiconductor films may be used.

[0153] In the light-emitting element shown in this embodiment, the second layer (hole transport layer) 112 is an embodiment of the present invention. Since it is formed using a fluorene derivative, not only is the device efficiency improved, but This allows for minimizing power consumption.

[0154] (Embodiment 3) This embodiment is a light-emitting element with a configuration in which multiple light-emitting units (also referred to as EL layers) are stacked. The following describes the configuration of the stacked element (hereinafter referred to as a stacked element) with reference to Figure 3. This light-emitting element is This is a stacked light-emitting element having multiple light-emitting units between a first electrode and a second electrode. The configuration of each light-emitting unit is the same as the configuration shown in Embodiment 2. Yes, it is possible. In other words, the light-emitting element shown in Embodiment 2 is a light-emitting element having one light-emitting unit. It is a child. In this embodiment, a light-emitting element having multiple light-emitting units will be described.

[0155] In Figure 3(A), a first light-emitting element is placed between the first electrode 521 and the second electrode 522. The knit 511 and the second light-emitting unit 512 are stacked. The first electrode 521 and the second Electrode 522 can be the same as in Embodiment 2. Also, the first light-emitting unit The second light-emitting unit 512 and the second light-emitting unit 512 may have the same configuration or a different configuration. The configuration can be the same as that of Embodiment 2.

[0156] When a voltage is applied to the first electrode 521 and the second electrode 522, the charge generation layer 513 generates a charge. In a layer in which electrons are injected into the light-emitting unit on one side and holes are injected into the light-emitting unit on the other side Yes, it can be a single layer or a configuration with multiple layers stacked on top of each other. Preferably, the structure consists of a layer for injecting holes and a layer for injecting electrons, stacked on top of each other.

[0157] The hole-injection layer includes molybdenum oxide, vanadium oxide, rhenium oxide, and rhodium oxide. Semiconductors or insulators such as thenium can be used. Alternatively, materials with high hole transport properties can be used. The configuration may also include an acceptor substance. The layer containing the terminating substance has 7,7,8,8-tetracyano-2 as the acceptor substance. 3,5,6-tetrafluoroquinodimethane (abbreviation: F4-TCNQ) and vanadium oxide It includes metal oxides such as molybdenum oxide and tungsten oxide. It is a substance with high hole transport properties. For example, aromatic amine compounds, carbazole derivatives, aromatic hydrocarbons, polymer compounds, and olivine Various compounds such as gomers, dendrimers, and polymers can be used. A fluorene derivative, which is one embodiment of the present invention shown in Form 1, can also be used in the same manner. Furthermore, a substance with high hole transport is defined as having a hole mobility of 10. -6 cm 2 / Vs or higher It is preferable to apply this. However, if the material has higher hole transport than electron transport, this Other materials may also be used. Composite materials containing a material with high hole transport properties and a material with acceptor properties. Because the material has excellent carrier injection and carrier transport properties, it enables low-voltage and low-current operation. It can be expressed.

[0158] The layer into which electrons are injected is an insulator such as lithium oxide, lithium fluoride, or cesium carbonate. Alternatively, semiconductors can be used. Or, a donor substance can be added to a material with high electron transport properties. The composition may also include added components. The donor substance may be an alkali metal or an alkaline earth element. Metals, rare earth metals, or metals belonging to Group 13 of the periodic table, and their oxides. Carbonates can be used. Specifically, lithium (Li), cesium (Cs), and methyl carbonates. Magnesium (Mg), Calcium (Ca), Ytterbium (Yb), Indium (In It is preferable to use lithium oxide, cesium carbonate, etc. Also, tetratianaphtha Organic compounds such as sen may be used as donor substances. Therefore, the materials shown in Embodiment 1 can be used. Therefore, the electron mobility is 10 -6 cm 2 It is preferable to apply values ​​that are greater than or equal to / Vs. However, other materials may be used as long as they have higher electron transport capabilities than holes. Composite materials having a substance with high electron transport properties and a donor substance have carrier implantation properties and carriers. Due to its excellent transportability, it can achieve low-voltage and low-current operation.

[0159] Furthermore, the electrode material shown in Embodiment 2 can also be used as the charge generation layer 513. For example, a combination of a material with high hole transport properties, a layer containing a metal oxide, and a transparent conductive film can be formed. It is permissible to do so. Furthermore, from the standpoint of light extraction efficiency, the charge generation layer 513 is made into a highly light-transmitting layer. It is preferable to do so.

[0160] In any case, the electric light sandwiched between the first light-emitting unit 511 and the second light-emitting unit 512 When a voltage is applied to the first electrode 521 and the second electrode 522, the charge generation layer 513 generates a charge on one side. This method involves injecting electrons into the light-emitting unit on one side and holes into the light-emitting unit on the other side. For example, the voltage should be such that the potential of the first electrode is higher than the potential of the second electrode. When applied, the charge generation layer 513 injects electrons into the first light-emitting unit 511, and the second Any configuration is acceptable as long as it injects holes into the light-emitting unit 512.

[0161] In this embodiment, a light-emitting element having two light-emitting units has been described, but similarly As shown in Figure 3(B), the same applies to light-emitting elements that stack three or more light-emitting units. It can be applied in various ways. As in the light-emitting element according to this embodiment, between a pair of electrodes By separating and arranging multiple light-emitting units with a charge generation layer 513, the current density is kept low. This allows for the realization of long-life elements in the high-brightness region. Furthermore, when lighting is used as an application example, Because the voltage drop due to the resistance of the electrode material can be reduced, uniform light emission over a large area becomes possible. Furthermore, it is possible to realize a light-emitting device that can be driven at low voltage and consumes low power.

[0162] Furthermore, by making the light-emitting color of each light-emitting unit different, the entire light-emitting element... This allows you to obtain light emission of the desired color. For example, a light-emitting element having two light-emitting units. In this configuration, the light-emitting color of the first light-emitting unit and the light-emitting color of the second light-emitting unit are in a complementary color relationship. By doing so, it is possible to obtain a light-emitting element that emits white light as a whole. Complementary colors are colors that, when mixed, result in achromatic colors. By mixing light obtained from a substance that emits a certain color, white light can be obtained. The same applies to the light-emitting element having three light-emitting units, for example, the first light-emitting unit The first light-emitting unit emits red light, the second light-emitting unit emits green light, and the third light-emitting unit emits green light. If the light-emitting color of the light-emitting element is blue, the entire light-emitting element can produce white light emission.

[0163] Furthermore, this embodiment can be appropriately combined with other embodiments.

[0164] (Embodiment 4) In this embodiment, a light-emitting device having the light-emitting element of the present invention in the pixel portion is shown in Figure 4. Let me explain. Figure 4(A) is a top view showing the light-emitting device, and Figure 4(B) is a modified version of Figure 4(A) A- These are cross-sectional views taken along A' and B-B'.

[0165] In Figure 4(A), the dotted line 401 is the drive circuit section (source-side drive circuit), 40 2 is the pixel section, and 403 is the drive circuit section (gate-side drive circuit). Also, 404 is the encapsulation substrate. , 405 is a sealing material, and the area inside the sealing material 405 is a space 407. .

[0166] The routing wiring 408 is connected to the source-side drive circuit 401 and the gate-side drive circuit 403. FPC (Flexible Printed Circuit) is a wiring used to transmit signals and serves as an external input terminal. (Lint circuit) Video signal, clock signal, start signal, reset signal from 409 Receives, etc. Note that only FPC is shown in the diagram here, but this FPC has print A circuit board (PWB) may be attached. Also, the light-emitting device in this specification may include This includes not only the light-emitting device itself, but also the state in which an FPC or PWB is attached to it. It shall be considered as such.

[0167] Next, the cross-sectional structure will be explained using Figure 4(B). The drive circuit is located on the element substrate 410. A section and a pixel section are formed, but here, the source-side drive circuit 401 is the drive circuit section. This shows one pixel in the pixel section 402. Note that the source-side drive circuit 401 is N-type A CMOS circuit is formed by combining a channel-type TFT423 and a P-channel-type TFT424. The drive circuit is made up of various CMOS, PMOS, or NMOS circuits. It may be formed. In this embodiment, a driver-integrated type in which the drive circuit is formed on the substrate is shown. However, this is not always necessary, and the drive circuit can be formed externally rather than on the circuit board.

[0168] Furthermore, the pixel section 402 includes a switching TFT 411 and a current control TFT 412 and It is formed by a plurality of pixels, each including a first electrode 413 electrically connected to a drain. Furthermore, an insulator 414 is formed to cover the end of the first electrode 413.

[0169] Furthermore, in order to ensure good coverage, the upper or lower end of the insulator 414 has a curvature. It is preferable to form a curved surface. For example, as the material of the insulator 414, positive By using a type of photosensitive acrylic, the radius of curvature (0.2 μm) is applied only to the upper end of the insulator 414. It is possible to give it a curved surface having a thickness of ~3 μm. Also, as an insulator 414, when exposed to light Negative type that becomes insoluble in etchant by light irradiation, or etchant that becomes insoluble by light irradiation A soluble, positive-type photosensitive material can be used.

[0170] An EL layer 416 and a second electrode 417 are formed on the first electrode 413, respectively. Here, the material used for the first electrode 413 can be various metals, alloys, or electrically conductive materials. Compounds and mixtures thereof can be used. Specific materials include: Using the material shown as usable for the first electrode in Embodiment 2 is It is assumed that this is possible.

[0171] Furthermore, the EL layer 416 can be coated using a vapor deposition method with a vapor deposition mask, an inkjet method, or a spin coat. It is formed by various methods such as the law. The EL layer 416 has the configuration shown in Embodiment 2. In addition, other materials constituting the EL layer 416 include low molecular weight compounds, or high molecular weight compounds. It may also be a sub-compound (including oligomers and dendrimers). Furthermore, the material used in the EL layer... In addition to organic compounds, inorganic compounds may also be used as materials.

[0172] Furthermore, various metals, alloys, and electrically conductive materials can be used for the second electrode 417. Compounds and mixtures thereof can be used. The second electrode 417 is used as the cathode. In that case, among them, metals, alloys, and electric materials with small work functions (work function of 3.8 eV or less) are selected. It is preferable to use gas-conductive compounds and mixtures thereof. For example, periodic compounds Elements belonging to Group 1 or Group 2 of the table, namely lithium (Li) and cesium (Cs), etc. Alkali metals, as well as magnesium (Mg), calcium (Ca), strontium ( Examples include alkaline earth metals such as Sr, and alloys containing them (MgAg, AlLi), etc. It is possible.

[0173] Furthermore, if the configuration is such that the light generated in the EL layer 416 passes through the second electrode 417, Electrode 417 of 2 consists of a thin metal film and a transparent conductive film (indium oxide-oxide). Indium oxide containing tin (ITO), silicon, or silicon oxide, indium oxide-tin oxide, indium oxide Indium oxide containing zinc oxide (IZO), tungsten oxide, and zinc oxide. It is also possible to use lamination with (etc.)

[0174] Furthermore, by bonding the sealing substrate 404 to the element substrate 410 with the sealing material 405 Light is emitted into the space 407 surrounded by the element substrate 410, the sealing substrate 404, and the sealing material 405. The structure is equipped with element 418. The space 407 is filled with a filler material. In addition to cases where an inert gas (such as nitrogen or argon) is filled, the sealant 405 is also used. In some cases, this may occur.

[0175] Furthermore, it is preferable to use epoxy resin for the sealing material 405. It is desirable that the material be as impermeable to moisture and oxygen as possible. Also, the encapsulation substrate 404 Materials used include glass substrates and quartz substrates, as well as FRP (Fiberglass Reinforced Plastic). Nforced Plastics, PVF (polyvinyl fluoride), polyester Alternatively, a plastic substrate made of acrylic or the like can be used.

[0176] As described above, an active matrix type light-emitting device having the light-emitting element of the present invention is obtained. It is possible.

[0177] Furthermore, the light-emitting element of the present invention is not only an active matrix type light-emitting device as described above, but also a It can also be used in a sibilance matrix type light-emitting device. Figure 5 shows an example of a light-emitting device using the present invention. Figure 5(A) shows a perspective view and a cross-sectional view of a passive matrix type light-emitting device. Figure 5(B) is a perspective view showing the optical device, and is a cross-sectional view obtained by cutting Figure 5(A) along the X and Y lines.

[0178] In Figure 5, an EL layer is placed between the first electrode 502 and the second electrode 503 on the substrate 501. 504 is provided. The end of the first electrode 502 is covered with an insulating layer 505. Furthermore, a partition layer 506 is provided on the insulating layer 505. The side walls of the partition layer 506 are on the substrate surface. The structure has an incline such that the distance between one side wall and the other side wall narrows as it approaches the edge. In other words, the cross-section of the partition layer 506 in the short-side direction is trapezoidal, and the base (in the plane direction of the insulating layer 505) The side facing the same direction as the insulating layer 505 (the side in contact with the insulating layer 505) is the upper side (the same direction as the plane of the insulating layer 505). It faces in the direction of the object and is shorter than the side that does not come into contact with the insulating layer 505. In this way, the partition layer 506 By providing this feature, defects in the light-emitting element caused by static electricity or other factors can be prevented.

[0179] As described above, a passive matrix type light-emitting device having the light-emitting element of the present invention can be obtained. can.

[0180] The light-emitting devices shown in this embodiment (active matrix type, passive matrix type) Since all types are formed using the light-emitting element with high luminescence efficiency of the present invention, the power consumption A light-emitting device with reduced power can be obtained.

[0181] In this embodiment 4, the configurations shown in embodiments 1 to 3 are combined as appropriate. It may be used.

[0182] (Embodiment 5) In this embodiment, an electronic device that includes the light-emitting device of the present invention shown in Embodiment 4 as a part thereof I will explain this. Electronic devices include cameras such as video cameras and digital cameras, goggles Display type, navigation system, sound playback device (car audio, audio) Computers, game consoles, and mobile information terminals (mobile computers, mobile phones, etc.), computers, game consoles, and personal digital assistants (mobile computers, mobile phones, etc.) (Telephone, portable game console or e-book, etc.), image playback device equipped with recording medium (specifically) It plays recording media such as Digital Versatile Discs (DVDs), and Examples include devices equipped with a display device capable of displaying images. An example is shown in Figure 6.

[0183] Figure 6(A) shows a television device according to one aspect of the present invention, comprising a housing 611, a support base 612, and a display. This television device includes a display unit 613, a speaker unit 614, a video input terminal 615, etc. The light-emitting device of the present invention can be applied to the display unit 613. Because it has the characteristic of being able to obtain high luminescence efficiency, the light-emitting device of the present invention is applicable. This allows for the creation of a television device with reduced power consumption.

[0184] Figure 6(B) shows a computer according to one aspect of the present invention, comprising a main body 621, a housing 622, and a front Display unit 623, keyboard 624, external connection port 625, pointing device 626 This includes the above. In this computer, the light-emitting device of the present invention is applied to the display unit 623. This is possible. The light-emitting device of the present invention has the characteristic of being able to obtain high luminous efficiency. Therefore, by applying the light-emitting device of the present invention, a computer with reduced power consumption can be obtained. It is possible.

[0185] Figure 6(C) shows a mobile phone according to one aspect of the present invention, comprising a main body 631, a housing 632, and a display unit. 633, audio input unit 634, audio output unit 635, operation keys 636, external connection port 637 , including antenna 638, etc. In this mobile phone, the display unit 633 has the light-emitting device of the present invention The device can be applied to the present invention. The present invention has the characteristic of being able to obtain high luminous efficiency. Because it has this property, by applying the light-emitting device of the present invention, a mobile phone with reduced power consumption can be achieved. You can obtain this.

[0186] Figure 6(D) shows a camera according to one aspect of the present invention, comprising a main body 641, a display unit 642, and a housing 6 43, external connection port 644, remote control receiver 645, image receiver 646, battery 647 This camera includes an audio input unit 648, operation keys 649, an eyepiece unit 650, etc. The light-emitting device of the present invention can be applied to the indicator part 642. The light-emitting device of the present invention is high Because it has the characteristic of being able to achieve high luminous efficiency, the light-emitting device of the present invention can be applied. This allows you to obtain a camera with reduced power consumption.

[0187] As described above, the application range of the light-emitting device of the present invention is extremely broad, and this light-emitting device can be used in all fields. It can be applied to electronic devices. By using the light-emitting device of the present invention, the power consumption is reduced. Electronic devices with reduced power consumption can be obtained.

[0188] Furthermore, the light-emitting device of the present invention can also be used as an illumination device. Figure 7 shows the present invention This is an example of a liquid crystal display device that uses an optical device as a backlight. The liquid crystal display device shown in Figure 7... The device has a housing 701, a liquid crystal layer 702, a backlight 703, and a housing 704, and the liquid crystal layer 70 2 is connected to the driver IC 705. Also, the backlight 703 is the present invention An optical device is used, and current is supplied via terminal 706.

[0189] By using the light-emitting device of the present invention as a backlight for a liquid crystal display device, A low-power backlight can be obtained. Furthermore, the light-emitting device of the present invention is a surface-emitting illumination device. Because it is possible to increase the area, it is also possible to increase the backlight area. Therefore, low power consumption. This allows for the creation of large-area liquid crystal display devices using electricity.

[0190] Figure 8 shows an example in which the light-emitting device to which the present invention is applied is used as a desk lamp, which is a lighting device. Yes. The desk lamp shown in Figure 8 has a housing 801 and a light source 802, and the light source 802 is The present invention is used in the light-emitting device. The present invention has a light-emitting element with high luminescence efficiency. Therefore, it can be used as a low-power desk lamp.

[0191] Figure 9 shows an example in which a light-emitting device to which the present invention is applied is used as an indoor lighting device 901. Since the light-emitting device of the present invention can be made to cover a large area, it can be used as a large-area lighting device. Furthermore, the light-emitting device of the present invention has a light-emitting element with high luminous efficiency, thus having low power consumption. It can be used as a power illumination device. In this way, a light-emitting device to which the present invention is applied can be used. In the room used as the indoor lighting device 901, as explained in Figure 6(A), the present invention relates to By installing the television device 902, you can watch public broadcasts and movies.

[0192] In this embodiment 5, the configurations shown in embodiments 1 to 4 are combined as appropriate. It may be used. [Examples]

[0193] <<Synthesis Example 1>> In this embodiment, the full form of the present invention, which is shown as general formula (G1) in Embodiment 1, is shown. The following shows an example of the synthesis of an olene derivative. Specifically, the 4 shown in structural formula (101) of Embodiment 1. -phenyl-4'-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: The synthesis method for BPAFLP is described below. The structure of BPAFLP is shown below.

[0194] [ka]

[0195] [Step 1: Synthesis method for 9-(4-bromophenyl)-9-phenylfluorene] In a 100 mL three-necked flask, add 1.2 g (50 mmol) of magnesium under reduced pressure for 30 minutes. After heating and stirring for several minutes, the magnesium was activated. After cooling to room temperature and then under a nitrogen atmosphere, Then, a few drops of dibromoethane were added and it was confirmed that foaming and heat were generated. Dehydrated diethyl ether was added to this. Slowly add 12 g (50 mmol) of 2-bromoviphenyl dissolved in 10 mL of water. The mixture was then heated under reflux and stirred for 2.5 hours to obtain the Grignard reagent.

[0196] 10 g (40 mmol) of 4-bromobenzophenone, 100 ml of anhydrous diethyl ether mL was placed in a 500 mL three-necked flask. The previously synthesized Grignard reagent was then slowly added to it. After adding the liquid dropwise, the mixture was heated and stirred under reflux for 9 hours.

[0197] After the reaction, the mixture was filtered to obtain a filtrate. The obtained filtrate was dissolved in 150 mL of ethyl acetate. However, 1N hydrochloric acid solution was added to this until it became acidic, and the mixture was stirred for 2 hours. The organic layer of this liquid The portion was washed with water, and magnesium sulfate was added to remove the moisture. This suspension was filtered, The resulting filtrate was concentrated to obtain a candy-like substance.

[0198] Next, in a 500 mL round-bottom flask, add this syrupy substance, 50 mL of glacial acetic acid, and 1 mL of hydrochloric acid. Add 0.0 mL and heat and stir under a nitrogen atmosphere at 130°C for 1.5 hours to allow the reaction to proceed.

[0199] After the reaction, the reaction mixture was filtered to obtain a filtrate. The obtained filtrate was mixed with water and sodium hydroxide. After washing with water, water, and methanol in that order, the product was dried to obtain a white powder of the target substance yielding 11 g. It was obtained at 69%. The reaction scheme of the above synthesis method is shown below (J-1).

[0200] [ka]

[0201] [Step 2: 4-phenyl-4'-(9-phenylfluoren-9-yl)triphenyl [Synthesis method for luamine (abbreviation: BPAFLP)] Add 9-(4-bromophenyl)-9-phenylfluorene to a 100 mL three-necked flask. 3.2g (8.0 mmol), 2.0g (8.0 mmol) of 4-phenyl-diphenylamine ol), sodium tert-butoxide 1.0g (10 mmol), bis(dibenzyl) Add 23 mg (0.04 mmol) of zylideneacetone palladium (0) to the flask. The atmosphere was purged with nitrogen. 20 mL of dehydrated xylene was added to this mixture. After degassing while stirring under reduced pressure, tri(tert-butyl)phosphine (10 wt%) 0.2 mL (0.1 mmol) of hexane solution was added. This mixture was then subjected to a nitrogen atmosphere. The mixture was heated and stirred at 110°C for 2 hours to allow it to react.

[0202] After the reaction, add 200 mL of toluene to the reaction mixture, and this suspension is mixed with Florizil and Se Filtered through a lite (Wako Pure Chemical Industries, Ltd., catalog number: 531-16855) The obtained filtrate was concentrated and subjected to silica gel column chromatography (eluent: toluene: Purification was performed using hexane (1:4). The resulting fraction was concentrated and mixed with acetone. After adding tanol and applying ultrasound, the mixture was recrystallized, yielding a white powder of the target substance in a yield of 4. It was obtained in 1 g with a yield of 92%. The reaction scheme of the above synthesis method is shown below (J-2).

[0203] [ka]

[0204] Rf values ​​in silica gel thin-layer chromatography (TLC) (developing solvent: ethyl acetate: Xane = 1:10) is the target product at 0.41, 9-(4-bromophenyl)-9-phenyl Fluorene had a value of 0.51, and 4-phenyl-diphenylamine had a value of 0.27.

[0205] The compounds obtained in step 2 above were measured by nuclear magnetic resonance (NMR). The results are as follows: This shows the regular data. Also, 1 The 1H NMR chart is shown in Figure 10. From the measurement results, the above structure The fluorene derivative of the present invention, BPAFLP (abbreviated), represented by formula (101), is obtained. It was discovered that...

[0206] 1 H NMR(CDCl3,300MHz):δ(ppm)=6.63-7.02(m , 3H), 7.06-7.11(m, 6H), 7.19-7.45(m, 18H), 7. 53-7.55(m, 2H), 7.75(d, J=6.9, 2H).

[0207] Furthermore, various physical properties of the obtained target material, BPAFLP (abbreviation), were measured as follows. did.

[0208] Absorption spectra (measurement range 200nm~800nm) are measured using a UV-Vis spectrophotometer (Japan) Measurements were taken using a Hikari Corporation V550 model. Figure 11 shows the absorption of toluene solution and thin film. This shows the vector. The horizontal axis represents wavelength (nm), and the vertical axis represents absorption intensity (arbitrary units). Toluene solution The liquid was measured in a quartz cell, and the spectrum was obtained by subtracting the absorption spectra of quartz and toluene. The diagram is shown. Furthermore, a sample of the thin film deposited on a quartz substrate was measured, and the absorption spectrum of the quartz was analyzed. The spectrum with the 'L' subtracted is shown in the diagram. From these spectral diagrams, the absorption peak on the longer wavelength side... In the case of toluene solution, it is observed at around 324 nm, and in the case of thin film, it is observed at around 314 nm. I found out that it can be seen.

[0209] The emission spectrum was measured using a fluorometer (FS920, Hamamatsu Photonics Ltd.). Figure 12 shows the emission spectra of the toluene solution and the thin film. The horizontal axis is wavelength (nm), and the vertical axis is... The value represents the luminescence intensity (in arbitrary units). The toluene solution was measured in a quartz cell, and the thin film was measured in a quartz cell. Samples deposited on a substrate were measured. From these spectral diagrams, the maximum emission wavelength was determined to be toluene. For solutions, the excitation wavelength is 386 nm (330 nm), and for thin films, it is 400 nm (excitation wave). It was found to be 349 nm long.

[0210] The thin film was measured in air using photoelectron spectroscopy (RIKEN Instruments Co., Ltd., AC-2), and the results showed that HOMO The level was -5.63 eV. From the Tauc plot of the thin film absorption spectrum, the absorption edge was It was 3.34 eV. Therefore, the energy gap in the solid state is estimated to be 3.34 eV. This means that the LUMO level is -2.29 eV. BPAFLP (abbreviation) has a relatively deep HOMO level and a wide band gap (Bg It was found that it has ).

[0211] The redox reaction characteristics were investigated by cyclic voltammetry (CV) measurement. This is an electrochemical analyzer (manufactured by BAS Corporation, model number: ALS Model 600A). (or 600C) was used.

[0212] The oxidation reaction characteristics were measured by changing the potential of the working electrode relative to the reference electrode from -0.10V to 1.50V. After scanning, measurements were taken by scanning from 1.50V to -0.10V. As a result, the HOMO level It was found to be -5.51 [eV]. Furthermore, the oxidation peak was still present even after 100 cycles. The values ​​were similar. This suggests that it is suitable for repeated oxidation-reduction between oxidized and neutral states. It was found to exhibit certain characteristics.

[0213] The measurement method will be described in detail below.

[0214] (Calculation of potential energy of the reference electrode relative to the vacuum level) First, the reference electrode used in this embodiment (Ag / Ag + Potential of the electrode relative to the vacuum level The energy (eV) was calculated. That is, Ag / Ag + The Fermi level of the electrode was calculated. The redox potential of ferrocene in methanol is +0.61 relative to a standard hydrogen electrode. It is known that 0[V vs. SHE] (Reference: Christian R.Goldsmith et al., J.Am.Chem.Soc., Vol. 124, No.1, 83-96, 2002). On the other hand, the reference electrode used in this embodiment is Then, when the redox potential of ferrocene in methanol was determined, it was found to be +0.11V[ vs. Ag / Ag + ] Therefore, the potential energy of this reference electrode is It was found that the voltage was 0.50 eV lower than that of a standard hydrogen electrode.

[0215] Here, the potential energy of the standard hydrogen electrode from the vacuum level is -4.44 eV. It is known that (Reference: Toshihiro Onishi and Tamami Koyama, Polymer EL Materials (Kyoritsu Shuppan)) (pp. 64-67). From the above, the potential of the reference electrode used with respect to the vacuum level is The energy was calculated to be -4.44 - 0.50 = -4.94 [eV].

[0216] (Conditions for measuring the CV of the target object) The solution used in CV measurement is dehydrated dimethylformamide (DMF) ((A Corporation)) as the solvent. Using Ludrich (99.8%, catalog number; 22705-6), the supporting electrolyte is Tetra-n-butylammonium perchlorate (n-Bu4NClO4) (manufactured by Tokyo Chemical Industry Co., Ltd.) Dissolve the product (catalog number; T0836) to a concentration of 100 mmol / L, and further... The sample to be measured was dissolved to a concentration of 2 mmol / L and prepared. Furthermore, the working electrode was used. For the first electrode, use a platinum electrode (PTE platinum electrode manufactured by BAS Corporation), and for the auxiliary electrode, use platinum Refer to the electrode (Pt counter electrode (5cm) for VC-3, manufactured by BAS Co., Ltd.). The electrode is Ag / Ag + Electrode (manufactured by BAS Corporation, RE7 non-aqueous solvent reference electrode) The following parameters were used: ) and the measurements were performed at room temperature (20-25°C). The scan speed was standardized to 0.1V / sec.

[0217] Next, the HOMO level was calculated from this CV measurement. Figure 1 shows the CV measurement results of the oxidation reaction characteristics. As shown in 3. As shown in Figure 13, the oxidation peak potential (from neutral to oxidation) E pa is 0.6 It was 2V. Also, the reduction peak potential (from the oxidizing side to the neutral side) was E pc The voltage was 0.52V. Therefore, the half-wave potential (E pa and E pc The potential midway between (Epa + Epc) / 2[V]) This can be calculated as 0.57V. + ] Electrical This indicates that it is oxidized by energy. Here, as mentioned above, the reference electrode used The potential energy for the vacuum level is -4.94 [eV], therefore BPAF The HOMO level of LP (abbreviation) is -4.94 - 0.57 = -5.51 [eV]. I found out.

[0218] The glass transition temperature is determined using a differential scanning calorimetry (DSC), manufactured by PerkinElmer. The measurement was performed using s1). From the measurement results, the glass transition temperature was 107°C. Thus It was found to exhibit a high glass transition temperature and good heat resistance. Furthermore, crystallization was observed. No peaks were observed, indicating that the substance is difficult to crystallize. [Examples]

[0219] ≪Synthesis Example 2≫ In this embodiment, the full form of the present invention, which is shown as general formula (G1) in Embodiment 1, is shown. Examples of olene derivative synthesis are shown. Specifically, the 4 shown in structural formula (151) of Embodiment 1 -phenyl-4'-[4-(9-phenylfluoren-9-yl)phenyl]triphenyl This section describes the synthesis method of luamine (abbreviated as BPAFLBi). The structure of BPAFLBi. The following is shown.

[0220] [ka]

[0221] [Step 1: Synthesis of 9-(4'-bromo-4-biphenyl)-9-phenylfluorene] Law] Place 5.1 g (22 mmol) of 2-bromoviphenyl into a 500 mL three-necked flask. After replacing the atmosphere inside the flask with nitrogen, add anhydrous tetrahydrofuran (THF) 20 Add 0 mL and bring the mixture to -78°C. Add 1.59 mol / L n-butyllithium to this mixture. 14 mL (22 mmol) of hexane solution was added dropwise, and the mixture was stirred for 2.5 hours. Add 6.7 g (20 mmol) of -benzoyl-4'-bromoviphenyl and bake at -78°C. The mixture was stirred for 2 hours and then at room temperature for 85 hours.

[0222] After the reaction, 1N dilute hydrochloric acid was added to the reaction solution until it became acidic, and the mixture was stirred for 4 hours. The material was washed with water. After washing, magnesium sulfate was added to remove the water. This suspension was filtered. The obtained filtrate was concentrated and subjected to silica gel column chromatography (eluent: toluene). Purification was carried out using hexane (1:1). The resulting fraction was concentrated and then treated with methanol. After adding [a certain substance] and applying ultrasound, the mixture was recrystallized to obtain the target substance as a white powder.

[0223] Next, in a 200 mL round-bottom flask, add this white powder, 50 mL of glacial acetic acid, and 1 mL of hydrochloric acid. Add 0 mL and heat and stir under a nitrogen atmosphere at 130°C for 2.5 hours to allow the reaction to proceed.

[0224] After the reaction, the reaction mixture was filtered to obtain a filtrate. The obtained filtrate was then mixed with 100 mL of toluene. Dissolve in water, wash in water, sodium hydroxide solution, and water in that order, add magnesium sulfate and remove moisture. Removed. This suspension was filtered, the resulting filtrate was concentrated, and acetone and methanol were added. After applying ultrasound and then recrystallizing, the target substance was obtained as a white powder with a yield of 6.3 g and a yield of 67 g. The result was obtained in %. The reaction scheme described above is shown below (J-3).

[0225] [ka]

[0226] [Step 2: 4-phenyl-4'-[4-(9-phenylfluoren-9-yl)phenyl Synthesis method of yltriphenylamine (abbreviation: BPAFLBi) Add 9-(4'-bromo-4-biphenyl)-9-phenyl phosphate to a 100 mL three-necked flask. 3.8g (8.0 mmol) of ruolene, 2.0g of 4-phenyl-diphenylamine ( 8.0 mmol), 1.0 g (10 mmol) of sodium tert-butoxide, Add 23 mg (0.04 mmol) of dibenzylideneacetone palladium (0), The atmosphere inside the flask was purged with nitrogen. 20 mL of anhydrous xylene was added to this mixture. The mixture is degassed while stirring under reduced pressure, and then tri(tert-butyl)phosphine ( 0.2 mL (0.1 mmol) of 10 wt% hexane solution was added. This mixture was then subjected to nitrogen. The mixture was heated and stirred at 110°C for 2 hours under controlled conditions to allow the reaction to occur.

[0227] After the reaction, add 200 mL of toluene to the reaction mixture, and this suspension is mixed with Florizil and Se The sample was filtered through a light source. The resulting filtrate was concentrated and subjected to silica gel column chromatography. Purification was performed using (eluent toluene:hexane = 1:4). The obtained fraction The solution was concentrated, acetone and methanol were added, and after ultrasonic treatment, it was recrystallized, and the desired result was obtained. A white powder of the substance was obtained in a yield of 4.4 g and 86%. The reaction scheme of the above synthesis method is shown below. As shown in (J-4).

[0228] [ka]

[0229] Rf values ​​in silica gel thin-layer chromatography (TLC) (developing solvent: ethyl acetate: Xane = 1:10) is the target product 0.51, 9-(4'-bromo-4-biphenyl)-9 -Phenylfluorene was 0.56 and 4-phenyl-diphenylamine was 0.28.

[0230] The compounds obtained in step 2 above were measured by nuclear magnetic resonance (NMR). The results are as follows: This shows the regular data. Also, 1 The 1H NMR chart is shown in Figure 14. From the measurement results, the above structure The present invention yields a fluorene derivative, BPAFLBi (abbreviated), represented by formula (151). It was discovered that this had happened.

[0231] 1 H NMR (CDCl3,300MHz): δ(ppm)=7.04(t, J=6. 6, 1H), 7.12-7.49(m, 30H), 7.55-7.58(m, 2H), 7 0.77 (d, J=7.8, 2H).

[0232] Furthermore, various physical properties of the obtained target product, BPAFLBi (abbreviation), were measured as follows. It was decided.

[0233] The absorption spectrum (measurement range 200nm~800nm) is measured using a UV-Vis spectrophotometer (JASCO). Measurements were taken using a V550 model (manufactured by [company name]). Figure 15 shows the absorption spectrum of toluene solution and thin film. This shows the absorption intensity. The horizontal axis represents wavelength (nm), and the vertical axis represents absorption intensity (arbitrary units). Toluene solution This is the spectrum obtained by measuring in a quartz cell and subtracting the absorption spectra of quartz and toluene. This is illustrated in the diagram. Furthermore, a thin film sample deposited on a quartz substrate was measured, and the absorption spectrum of the quartz was obtained. The spectra after subtracting are shown in the diagram. From these spectral diagrams, the absorption peak on the long wavelength side is In the case of a toluene solution, it is observed at around 340 nm, and in the case of a thin film, it is observed at around 341 nm. I found out that it is possible.

[0234] The emission spectrum was measured using a fluorometer (FS920, Hamamatsu Photonics Ltd.). Figure 16 shows the emission spectra of the toluene solution and the thin film. The horizontal axis is wavelength (nm), and the vertical axis is... The value represents the luminescence intensity (in arbitrary units). The toluene solution was measured in a quartz cell, and the thin film was measured in a quartz cell. Samples deposited on a substrate were measured. From these spectral diagrams, the maximum emission wavelength was determined to be toluene. For solutions, the excitation wavelength is 386 nm (345 nm); for thin films, it is 399 and 419 nm. (The excitation wavelength was found to be 348 nm.)

[0235] The thin film was measured in air using photoelectron spectroscopy (RIKEN Instruments Co., Ltd., AC-2), and the results showed that HOMO The level was -5.64 eV. From the Tauc plot of the thin film absorption spectrum, the absorption edge was It was 3.28 eV. Therefore, the energy gap in the solid state is estimated to be 3.28 eV. This means that the LUMO level is -2.36 eV. BPAFLBi (abbreviation) has a relatively deep HOMO level and a wide band gap (B It was found that it possesses g).

[0236] The redox reaction characteristics were investigated by cyclic voltammetry (CV) measurement. This is an electrochemical analyzer (manufactured by BAS Corporation, model number: ALS Model 600A). (or 600°C) was used. The measurement method is the same as in Example 1, so the explanation will be omitted. ru.

[0237] The oxidation reaction characteristics were measured by changing the potential of the working electrode relative to the reference electrode from -0.10V to 1.50V. After scanning, measurements were taken by scanning from 1.50V to -0.10V. As a result, the HOMO level It was found to be -5.49 [eV]. Furthermore, the oxidation peak was still present even after 100 cycles. The values ​​were similar. This suggests that it is suitable for repeated oxidation-reduction between oxidized and neutral states. It was found to exhibit certain characteristics.

[0238] Figure 17 shows the CV measurement results for the oxidation reaction characteristics.

[0239] The glass transition temperature is determined using a differential scanning calorimetry (DSC), manufactured by PerkinElmer. The measurement was performed using s1). From the measurement results, the glass transition temperature was 126°C. Thus It was found to exhibit a high glass transition temperature and good heat resistance. Furthermore, crystallization was observed. No peaks were observed, indicating that the substance is difficult to crystallize. [Examples]

[0240] In this example, the fluorene derivative synthesized in Example 1 is 4-phenyl-4'-(9 Using -phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP) The fabrication method of the formed light-emitting element and the measurement results of its element characteristics are shown.

[0241] The element structure of the light-emitting element in this embodiment is as shown in Figure 18. Light-emitting element 2 The hole transport layer 1512 contains the fluorene derivative of the present invention described above (abbreviated as BPAFLP). It was formed using the following. In addition, the light-emitting element 1, which is a comparative light-emitting element, has a hole transport layer 151 2. 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: Formed using NPB, and identical to the substrate on which the light-emitting element 2 is formed in order to standardize the comparison conditions. A comparison light-emitting element 1 was formed on the substrate and compared with light-emitting element 2. The structural formula of the compound is shown below.

[0242] [ka]

[0243] First, on the glass substrate substrate 1501, indium oxide-tin oxide containing silicon oxide is added. The first electrode 1502 was formed by depositing a film using the sputtering method. The film thickness was 1 The wavelength was set to 10 nm, and the electrode area was set to 2 mm × 2 mm.

[0244] Next, an EL layer 1503 is formed by stacking multiple layers on the first electrode 1502. In Example 5, the EL layer 1503 is a hole injection layer, and the first layer 1511 is a hole transport layer. A second layer 1512, a third layer 1513 which is an emissive layer, and a fourth layer 15 which is an electron transport layer. 14. It has a structure in which a fifth layer 1515, which is an electron injection layer, is sequentially stacked.

[0245] The first electrode 1502 is formed such that the surface on which the first electrode 1502 is formed faces downwards. The prepared substrate is fixed to a substrate holder provided inside the vacuum deposition apparatus, 10 -4 Reduced to approximately Pa After applying pressure, 4,4'-bis[N-(1-naphthyl)-N-fe Co-depositing of [nylaminobiphenyl] (abbreviation: NPB) and molybdenum(VI) oxide. This formed the first layer 1511, which is a hole injection layer. Its film thickness was set to 50 nm, and NP The ratio of B to molybdenum(VI) oxide is 4:1 by weight = (NPB: molybdenum oxide) The deposition rate was adjusted to achieve this. Note that co-deposition is a method in which multiple materials are deposited in a single processing chamber. This is a vapor deposition method that simultaneously deposits and forms a film.

[0246] Next, a hole-transporting material is deposited onto the first layer 1511 using a resistive heating deposition method. A film was deposited to a thickness of m, forming a second layer 1512 which is a hole transport layer. When forming the comparative light-emitting element 1, 4,4'-bis[N-(1-naphthyl)-N-pheny When using [diaminobiphenyl] (abbreviated as NPB) to form the light-emitting element 2, 4-f Phenyl-4'-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BP) Each was formed using AFLP.

[0247] Next, a third layer, which is an emissive layer, is deposited on the second layer 1512 using a vapor deposition method with resistance heating. Formed 1513. 9-[4-(10-phenyl-9-antryl)phenyl]-9H -Carbazole (abbreviated as CzPA) and 4-(10-phenyl-9-anthryl)-4'- (9-phenyl-9H-carbazole-3-yl)triphenylamine (abbreviation: PCBA) A third layer 1513 was formed with a thickness of 30 nm by co-depositing PA. The weight ratio of CzPA to PCBAPA is 1:0.10 = (CzPA:PCBAPA) The deposition rate was adjusted to achieve the desired result.

[0248] Furthermore, using a resistive heating deposition method, tris(8-quinolino) was deposited onto the third layer 1513. Aluminum(III) (abbreviated as Alq) is layered at 10 nm, and then bathophenantho is placed on top of it. A phosphorus (abbreviated as BPhen) film was deposited to a thickness of 20 nm, forming the fourth electron transport layer. This formed layer 1514.

[0249] A lithium fluoride (LiF) film is deposited on the fourth layer 1514 to a thickness of 1 nm. By doing so, a fifth layer 1515, which is an electron injection layer, was formed.

[0250] Finally, using a resistive heating deposition method, aluminum was deposited to a thickness of 200 nm. By forming a film, a second electrode 1504 is created, and the comparative light-emitting element 1 and light-emitting element 2 are fabricated. did.

[0251] Note that comparison light-emitting element 1 and light-emitting element 2 were manufactured using the same process, except for the second layer 1512. It is.

[0252] The comparative light-emitting element 1 and light-emitting element 2 obtained above were placed in a glove box under a nitrogen atmosphere. After sealing the light-emitting elements inside the container to prevent them from being exposed to the atmosphere, these The operating characteristics of the optical element were measured. The measurements were taken at room temperature (maintained at 25°C). I went there.

[0253] Figure 19 shows the current density-luminance characteristics of comparative light-emitting element 1 and light-emitting element 2. Also, voltage- The luminance characteristics are shown in Figure 20, and the luminance-current efficiency characteristics are shown in Figure 21. In Figure 19, the vertical axis is luminance. degrees (cd / m 2 ), with current density (mA / cm²) on the horizontal axis. 2 ) is shown, and in Figure 20 the vertical axis is luminance (c d / m 2 In Figure 21, the vertical axis shows current efficiency (cd / A), and the horizontal axis shows voltage (V). Brightness (cd / m²) 2 It also shows 1000 cd / cm². 2 Voltage of the light-emitting element in the vicinity Chromaticity and current efficiency are shown in Table 1.

[0254] [Table 1]

[0255] When the driving voltage of the light-emitting element 2 is 4.2V, the brightness is 880 cd / m². 2 The current value is 0.41 It was mA. Compared to the comparison light-emitting element 1 which uses an NPB in the second layer 1512, the second It was found that the light-emitting element 2, which uses BPAFLP (abbreviated) in layer 1512, has high current efficiency. This is because the carrier balance of light-emitting element 2 is improved compared to light-emitting element 1. This is thought to be because the HOMO level of BPAFLP (abbreviation) is generated (compared to NPB). Because the HOMO level is close to that of the host material CzPA (abbreviated) in the photolayer, light is emitted from the hole transport layer. This is thought to be due to improved hole injection into the layer. Furthermore, (compared to NPB) B In PAFLP (abbreviated), the LUMO level is high, causing electron blocking from the emissive layer to the hole transport layer. This is thought to be due to improved grip. Furthermore, (compared to NPB) BPAFLP ( Because the band gap (Bg) of the abbreviated layer is wide, excitation occurs in the third layer 1513 (luminescent layer). The starter was trapped (not extinguished) without moving to the adjacent second layer 1512. It can be folded. [Examples]

[0256] In this example, the fluorene derivative synthesized in Example 1 is 4-phenyl-4'-(9 Using -phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP) The fabrication method of the formed light-emitting element and the measurement results of its element characteristics are shown.

[0257] The element structure of the light-emitting element 3 in this embodiment is as shown in Figure 18, and hole transport Layer 1512 is formed using the fluorene derivative of the present invention described above (abbreviated as BPAFLP). It is as follows. The structural formula of the organic compound used in this embodiment is shown below.

[0258] [Chemical formula]

[0259] First, indium tin oxide containing silicon oxide was formed into a film on a substrate 1501 which is a glass substrate by sputtering, and a first electrode 1502 was formed. The film thickness was set to 1 10 nm, and the electrode area was set to 2 mm × 2 mm.

[0260] Next, an EL layer 1503 in which a plurality of layers are stacked is formed on the first electrode 1502. In this embodiment, the EL layer 1503 has a structure in which a first layer 1511 which is a hole injection layer, a second layer 1512 which is a hole transport layer, a third layer 1513 which is a light emitting layer, a fourth layer 151 4 which is an electron transport layer, and a fifth layer 1515 which is an electron injection layer are sequentially stacked.

[0261] The substrate on which the first electrode 1502 is formed is fixed to a substrate holder provided in a vacuum evaporation apparatus so that the surface on which the first electrode 1502 is formed faces downward, and the pressure is reduced to about 10 Pa, and then 9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA) and molybdenum(VI) oxide are co-evaporated -4 onto the first electrode 1502 to form a first layer 1511 which is a hole injection layer. The film thickness was set to 50 nm, and the ratio of CzPA to molybdenum(VI) oxide was adjusted so that the deposition rate was such that the weight ratio was 4:1 = (CzPA: molybdenum oxide).

[0262] Next, a hole transporting material was deposited on the first layer 1511 by a deposition method using resistance heating to a thickness of 10 n A film was deposited to a thickness of m, forming a second layer 1512 which is a hole transport layer. When forming the optical element 3, 4-phenyl-4'-(9-phenylfluorene-9-i Formed using triphenylamine (abbreviation: BPAFLP).

[0263] Next, a third layer, which is an emissive layer, is deposited on the second layer 1512 using a vapor deposition method with resistance heating. Formed 1513. 9-[4-(10-phenyl-9-antryl)phenyl]-9H -Carbazole (abbreviated as CzPA) and 4-(10-phenyl-9-anthryl)-4'- (9-phenyl-9H-carbazole-3-yl)triphenylamine (abbreviation: PCBA) A third layer 1513 was formed with a thickness of 30 nm by co-depositing PA. The weight ratio of CzPA to PCBAPA is 1:0.10 = (CzPA:PCBAPA) The deposition rate was adjusted to achieve the desired result.

[0264] Subsequently, similar to the comparative light-emitting element 1, a fourth layer which is an electron transport layer and a fifth layer which is an electron injection layer are formed. A layer and a second electrode were formed to create the light-emitting element 3.

[0265] The light-emitting element 3 obtained as described above is placed in a glove box under a nitrogen atmosphere. After sealing the device to prevent exposure to the atmosphere, the operating characteristics of the light-emitting element 3 were measured. The measurements were taken at room temperature (in an atmosphere maintained at 25°C).

[0266] Figure 22 shows the current density-luminance characteristics of the light-emitting element 3. Figure 23 shows the voltage-luminance characteristics. The luminance-current efficiency characteristics are shown in Figure 24. In Figure 22, the vertical axis is luminance (cd / m²). 2 ),beside Current density (mA / cm²) on the axis 2 Figure 23 shows the luminance (cd / m²) on the vertical axis.2 ) On the horizontal axis, voltage (V) is shown. In FIG. 24, on the vertical axis, current efficiency (cd / A) is shown, and on the horizontal axis, luminance (cd / m ) is shown. Also, the voltage, chromaticity, and current efficiency of the light-emitting element around 1000 cd / m 2 ) are shown in Table 2. Near 1000 cd / m 2 is shown in Table 2. is shown.

[0267] [Table 2]

[0268] According to this example, it was confirmed that the light-emitting element formed using the fluorene derivative (abbreviation: BPAFLP) of the present invention has characteristics as a light-emitting element and functions sufficiently. Also, from the results of the reliability test, it was found that even when the light-emitting element was continuously lit, no short circuit occurred due to film defects or the like, and a highly reliable light-emitting element was obtained. was obtained.

[0269] 2 Regarding the light-emitting element 3, with an initial luminance of 1000 cd / cm as shown in FIG. 25 (the vertical axis is the relative luminance when 1000 cd / cm 2 is taken as 100%). From the results of FIG. 25, it was found that the light-emitting element 3 maintained a luminance of 78% of the initial luminance even after 1000 hours and has a long lifespan. Therefore, it was found that by applying the BPA FLP (abbreviation) of the present invention, a long-life light-emitting element can be obtained. FLP (abbreviation) of the present invention, it was found that a long-life light-emitting element can be obtained. was found. was found. [Example]

[0270] In this example, 4 -phenyl-4’-[4-(9-phenylfluorene-9-yl)phenyl]triphenyl Light-emitting element formed using ruamine (abbreviation: BPAFLBi), 4-phenyl-4'-( Using 9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP) The fabrication method and resulting characteristics of the light-emitting element formed are shown.

[0271] The element structure of the light-emitting element in this embodiment is as shown in Figure 18, and the hole injection layer The hole transport layer is formed using the fluorene derivative of the present invention described above. The structural formula of the organic compound used in Example 5 is shown below.

[0272] [ka]

[0273] First, on the glass substrate substrate 1501, indium oxide-tin oxide containing silicon oxide is added. The first electrode 1502 was formed by depositing a film using the sputtering method. The film thickness was 11 The wavelength was set to 0 nm, and the electrode area was set to 2 mm × 2 mm.

[0274] Next, an EL layer 1503 is formed by stacking multiple layers on the first electrode 1502. In this example, the EL layer 1503 is a hole injection layer, the first layer 1511 is a hole transport layer, and The second layer 1512, the third layer 1513 which is a light-emitting layer, and the fourth layer 151 which is an electron transport layer. 4. The structure has a fifth layer 1515, which is an electron injection layer, stacked sequentially.

[0275] The first electrode 1502 is formed such that the surface on which the first electrode 1502 is formed faces downwards. The prepared substrate is fixed to a substrate holder provided inside the vacuum deposition apparatus, 10 -4 Reduced to approximately Pa After pressing, a fluorene derivative and molybdenum oxide, according to one aspect of the present invention, are placed on the first electrode 1502. By co-depositing with butene(VI), a first layer 1511, which is a hole injection layer, was formed. The film thickness is 50 nm, and the ratio of the fluorene derivative to molybdenum(VI) oxide is The deposition rate was adjusted so that the weight ratio was 4:1 = (fluorene derivative: molybdenum oxide). The section was removed. Furthermore, when forming the light-emitting element 4 as the fluorene derivative, 4-Fe Nyl-4'-[4-(9-phenylfluoren-9-yl)phenyl]triphenylamine When using (abbreviation: BPAFLBi) to form the light-emitting element 5, 4-phenyl-4 -(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP) They were formed using [the appropriate method / tool].

[0276] Next, a hole transport material is deposited on the first layer to a thickness of 10 nm using a deposition method with resistance heating. The film was formed in such a manner, and a second layer 1512, which is a hole transport layer, was created. When forming, BPAFLBi is used, and when forming the light-emitting element 5, BPAFL Each was formed using P.

[0277] Next, a third layer, which is an emissive layer, is deposited on the second layer 1512 using a vapor deposition method with resistance heating. 1513 was formed. In this embodiment, the light-emitting layer consisted of two layers. 9-[4-(10- Phenyl-9-antryl)phenyl]-9H-carbazole (abbreviation: CzPA) and 4- (10-phenyl-9-anthryl)-4'-(9-phenyl-9H-carbazole-3) By co-depositing with -yl)triphenylamine (abbreviation: PCBAPA), the second A first light-emitting layer was formed on layer 1512 with a thickness of 15 nm. Here, CzPA and PCBA were used. The deposition rate should be such that the weight ratio with PA is 1:0.10 = (CzPA:PCBAPA). I adjusted it.

[0278] Next, a second light-emitting layer was formed on the first light-emitting layer by a vapor deposition method using resistance heating. 9 -[4-(10-phenyl-9-antryl)phenyl]-9H-carbazole (abbreviation: CzPA) and 4-(10-phenyl-9-anthryl)-4'-(9-phenyl-9H- Co-depositing with carbazole-3-yl)triphenylamine (abbreviation: PCBAPA) Thus, a first light-emitting layer was formed on the second layer 1512 with a thickness of 15 nm. Here, C The weight ratio of zPA to PCBA is 1:0.05 = (CzPA:PCBAPA). The deposition rate was adjusted accordingly.

[0279] Subsequently, similar to the comparative light-emitting element 1, a fourth layer which is an electron transport layer and a fifth layer which is an electron injection layer are formed. Layers and second electrodes were formed, respectively, to fabricate light-emitting elements 4 and 5.

[0280] Note that the light-emitting element 4 and the light-emitting element 5 are located in layers other than the first layer 1511 and the second layer 1512. They are produced using the same process.

[0281] Based on the above, the obtained light-emitting elements 4 and 5 were placed in a glove box under a nitrogen atmosphere. Inside, after sealing the light-emitting elements to prevent them from being exposed to the atmosphere, these light-emitting elements The operating characteristics of the element were measured. The measurements were taken at room temperature (in an atmosphere maintained at 25°C). went.

[0282] Figure 26 shows the current density-luminance characteristics of light-emitting elements 4 and 5. Also, the voltage-luminance characteristics are shown. The characteristics are shown in Figure 27, and the luminance-current efficiency characteristics are shown in Figure 28. In Figure 26, the vertical axis is luminance ( cd / m 2 ), with current density (mA / cm²) on the horizontal axis.2 ) is shown, and in Figure 27 the vertical axis is luminance (cd / m 2 In Figure 28, the horizontal axis shows voltage (V), and the vertical axis shows current efficiency (cd / A), while the horizontal axis shows brightness. degrees (cd / m 2 It also indicates 1000 cd / m². 2 Voltage and chromaticity of light-emitting elements in the vicinity The current efficiency and external quantum efficiency are shown in Table 3.

[0283] [Table 3]

[0284] This embodiment shows a light-emitting element formed using BPAFLBi (abbreviation) and BPAFLP. The child was confirmed to have the characteristics required for a light-emitting element and to function adequately. Furthermore, reliability tests were conducted. The results show that even when the light-emitting element is continuously lit, a short circuit occurs due to defects in the film, etc. It was found that a highly reliable light-emitting element was obtained without any problems.

[0285] Furthermore, regarding the light-emitting elements 4 and 5, the initial brightness is set to 1000 cd / cm². 2 as, Figure 29 shows the results of a continuous lighting test using low current drive (vertical axis: 1000 cd / c m 2 (This is the relative brightness when set to 100%). From the results in Figure 29, the light-emitting element 4 is 850°C. Even after 850 hours, the brightness remains at 74% of the initial brightness, and the light-emitting element 5 maintains 75% of its initial brightness. It was found to have a long lifespan. Therefore, the BPAFLBi (abbreviation) of the present invention and It has been found that by applying BPAFLP (abbreviation), long-life light-emitting elements can be obtained. . [Examples]

[0286] In this example, the fluorene derivative of the present invention, 4-phenyl-4, was synthesized in Example 1. -(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP) This document describes the fabrication method and resulting characteristics of a light-emitting element formed using [the specified method].

[0287] The element structure of the light-emitting element in this embodiment is as shown in Figure 18, and the light-emitting element 6 This is formed using the fluorene derivative of the present invention described above in the hole transport layer. The structural formulas of the organic compounds used in the examples are shown below.

[0288] [ka]

[0289] First, on the glass substrate substrate 1501, indium oxide-tin oxide containing silicon oxide is added. The first electrode 1502 was formed by depositing a film using the sputtering method. The film thickness was 1 The wavelength was set to 10 nm, and the electrode area was set to 2 mm × 2 mm.

[0290] Next, an EL layer 1503 is formed by stacking multiple layers on the first electrode 1502. In Example 5, the EL layer 1503 is a hole injection layer, and the first layer 1511 is a hole transport layer. A second layer 1512, a third layer 1513 which is an emissive layer, and a fourth layer 15 which is an electron transport layer. 14. It has a structure in which a fifth layer 1515, which is an electron injection layer, is sequentially stacked.

[0291] The first electrode 1502 is formed such that the surface on which the first electrode 1502 is formed faces downwards. The prepared substrate is fixed to a substrate holder provided inside the vacuum deposition apparatus, 10 -4 Reduced to approximately Pa After applying pressure, 4,4'-bis[N-(1-naphthyl)-N-fe Co-depositing of [nylaminobiphenyl] (abbreviation: NPB) and molybdenum(VI) oxide. This formed the first layer 1511, which is a hole injection layer. Its film thickness was set to 50 nm, and NP The ratio of B to molybdenum(VI) oxide is 4:2 by weight = (NPB: molybdenum oxide) The deposition rate was adjusted accordingly. Note that co-deposition is a method that uses multiple evaporation sources within a single processing chamber. This is a vapor deposition method in which deposition is performed simultaneously from two locations.

[0292] Next, a hole-transporting material is deposited onto the first layer 1511 using a resistive heating deposition method. A film was deposited to a thickness of m, forming a second layer 1512 which is a hole transport layer. When forming the optical element 6, 4-phenyl-4'-(9-phenylfluorene-9-i When using triphenylamine (abbreviation: BPAFLP) to form the comparative light-emitting element 7 It contains 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviated) Each was formed using :NPB).

[0293] Next, a third layer, which is an emissive layer, is deposited on the second layer 1512 using a vapor deposition method with resistance heating. 1513 was formed. 3-phenyl-9-[4-(5-phenyl-1,3,4-oxadi Azole-2-yl)phenyl]-9H-carbazole (abbreviation: CO11II) and (2- Phenylpyridinato-N,C 2’ ) Iridium(III) acetylacetonate (abbreviation: By co-depositing Ir(ppy)2acac, the third layer 913 is made with a thickness of 40 nm. It was formed as follows. Here, the weight ratio of CO11II to Ir(ppy)2acac is 1:0. The deposition rate was adjusted so that 08 = (CO11II:Ir(ppy)2acac). .

[0294] Furthermore, a vapor deposition method using resistance heating was applied to the third layer 1513, using bis(2-methyl-8) -Quinolinolato)(4-phenylphenolato)aluminum(III) (abbreviation: BAlq) ) is 10nm thick, and bathophenanthroline (abbreviation: BPhen) is applied on top of that to create a 20nm film thickness. The film was deposited in this manner to form a fourth layer 1514, which is an electron transport layer.

[0295] Subsequently, similar to the comparative light-emitting element 1, a fourth layer which is an electron transport layer and a fifth layer which is an electron injection layer are formed. Layers and a second electrode were formed to create the light-emitting element 6 and the comparative light-emitting element 7.

[0296] Furthermore, the light-emitting element 6 and the comparative light-emitting element 7 were manufactured using the same process, except for the second layer 1512. Yes, they are.

[0297] The light-emitting element 6 and comparative light-emitting element 7 obtained above were placed in a glove box under a nitrogen atmosphere. Inside, after sealing the light-emitting elements to prevent them from being exposed to the atmosphere, these light-emitting elements The operating characteristics of the element were measured. The measurements were taken at room temperature (in an atmosphere maintained at 25°C). went.

[0298] Figure 30 shows the current density-luminance characteristics of the light-emitting element 6 and the comparative light-emitting element 7. Also shown is the voltage-luminance characteristics. The characteristics are shown in Figure 31, and the luminance-current efficiency characteristics are shown in Figure 32. In Figure 30, the vertical axis is luminance ( cd / m 2 ), with current density (mA / cm²) on the horizontal axis. 2 ) is shown, and in Figure 31 the vertical axis is luminance (cd / m 2 In Figure 32, the horizontal axis shows voltage (V), and the vertical axis shows current efficiency (cd / A), while the horizontal axis shows brightness. degrees (cd / m 2 It also indicates 1000 cd / m². 2 Voltage and chromaticity of light-emitting elements in the vicinity The current efficiency and external quantum efficiency are shown in Table 4.

[0299] [Table 4]

[0300] Figure 33 also shows the emission spectra of the light-emitting element 6 and the comparative light-emitting element 7.

[0301] As shown in Figure 33, in the comparative light-emitting element 7, in addition to the light emission originating from the dopant, the hole transport layer... A specific emission wavelength originating from a certain NPB was observed. This indicates that NPBs have the ability to block electrons. This indicates that even in NPBs with low internal quantum efficiency, some recombination is occurring. As a result, it is thought that the current efficiency and external quantum efficiency decreased. Furthermore, NPB is triplet excitation. Because the energy is low, the triplet excitation energy in the light-emitting layer is transferred to the NPB. This is thought to have resulted in lower current efficiency and external quantum efficiency. On the other hand, in the light-emitting element 6, Only luminescence originating from the dopant in the luminescence layer was observed, and BPAFLP (abbreviated) in the hole transport layer was observed. No emission was observed. Therefore, BPAFLP has a high ability to block electrons. The above suggests that the triplet excitation energy is also large. As a result, the excitation energy produced The current is mainly consumed by the dopant, which is a phosphorescent material in the light-emitting layer, and is converted into light, resulting in high current efficiency. It can be said that this was achieved. Thus, BPAFLP (abbreviated) in one aspect of the present invention is used in the hole transport layer. It was found that using this method could result in highly efficient components. [Examples]

[0302] In this example 7, the fluorene derivative synthesized in Example 1 is 4-phenyl-4'-( Using 9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP) The method for fabricating the light-emitting element and the measurement results of its element characteristics are shown.

[0303] The element structure of the light-emitting elements 8-10 in this embodiment 7 is as shown in Figure 18. The light-emitting element 9 is connected to the hole transport layer, and the light-emitting element 10 is connected to the hole injection layer and the hole transport layer as described above. These were formed using the fluorene derivatives of the present invention. The organic compound used in Example 7 The structural formula of the compound is shown below.

[0304] [ka]

[0305] First, on the glass substrate substrate 1501, indium oxide-tin oxide containing silicon oxide is added. The first electrode 1502 was formed by depositing a film using the sputtering method. The film thickness was 11 The wavelength was set to 0 nm, and the electrode area was set to 2 mm × 2 mm.

[0306] Next, an EL layer 1503 is formed by stacking multiple layers on the first electrode 1502. In this example, the EL layer 1503 is a hole injection layer, the first layer 1511 is a hole transport layer, and The second layer 1512, the third layer 1513 which is a light-emitting layer, and the fourth layer 151 which is an electron transport layer. 4. The structure has a fifth layer 1515, which is an electron injection layer, stacked sequentially.

[0307] The first electrode 1502 is formed such that the surface on which the first electrode 1502 is formed faces downwards. The prepared substrate is fixed to a substrate holder provided inside the vacuum deposition apparatus, 10 -4 Reduced to approximately Pa After pressing, a hole injection material is deposited on the first electrode 1502 to a thickness of 50 nm. Then, a first layer 1511, which is a hole injection layer, was formed. Furthermore, the light-emitting elements 8 and 9 were When forming, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]bifu Hole implantation is achieved by co-depositing phenyl (abbreviated as NPB) and molybdenum(VI) oxide. A first layer, layer 1511, was formed. Its film thickness was set to 50 nm, and it was composed of NPB and molybdenum oxide. The ratio of (VI) is such that the weight ratio is 4:2 = (NPB: molybdenum oxide) when the vapor deposition is performed. The phosphate was adjusted. Also, when forming the light-emitting element 10, 4-phenyl-4'-(9- Phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP) and molybdenum oxide By co-depositing with butene(VI), a first layer 1511, which is a hole injection layer, is formed. The film thickness was set to 50 nm, and the ratio of BPAFLP to molybdenum(VI) oxide was, by weight. The deposition rate was adjusted so that the ratio was 4:1 (BPAFLP: molybdenum oxide).

[0308] Next, a hole-transporting material is deposited onto the first layer 1511 using a resistive heating deposition method. A film was deposited to a thickness of m, forming a second layer 1512 which is a hole transport layer. When forming the optical element 8, 4-phenyl-4'-(9-phenyl-9H-carbazo Using (-3-yl)triphenylamine (abbreviation: PCBA1BP), 9 light-emitting elements When forming the light-emitting element 10, 4-phenyl-4'-(9-phenylfluorene- Each was formed using 9-yl)triphenylamine (abbreviated as BPAFLP).

[0309] Next, a third layer, which is an emissive layer, is formed on the second layer using a vapor deposition method with resistance heating. In this example, 3-phenyl-9-[4-(5-phenyl-1,3,4-oxadia Zole-2-yl)phenyl]-9H-carbazole (abbreviation: CO11II) and 4-phenyl Nyl-4'-(9-phenyl-9H-carbazole-3-yl)triphenylamine (abbreviated) Name: PCBA1BP) and bis{2-(4-fluorophenyl)-3,5-dimethylpyridine Nato(picolinato) iridium(III) (abbreviation: Ir(dmFppr)2pic) and A third layer with a thickness of 40 nm was formed by co-depositing CO11II and The weight ratio of PCBA1BP to Ir(dmFppr)2pic is 1:0.15:0.1 = (CO11II:PCBA1BP:Ir(dmFppr)2pic) I adjusted the settings.

[0310] Subsequently, similar to the comparative light-emitting element 1, a fourth layer which is an electron transport layer and a fifth layer which is an electron injection layer are formed. Layers and a second electrode were formed to create light-emitting elements 8 to 10.

[0311] Note that, except for the first layer 1511 and the second layer 1512, the light-emitting elements 8 to 10 are... They are produced using the same process.

[0312] The light-emitting elements 8 to 10 obtained as described above are placed in a glove box in a nitrogen atmosphere. Then, after sealing the light-emitting elements to prevent them from being exposed to the atmosphere, these light-emitting elements The operating characteristics were measured. The measurements were taken at room temperature (maintained at 25°C). Ta.

[0313] Figure 34 shows the current density-luminance characteristics of light-emitting elements 8 to 10. Also, the voltage-luminance characteristics are shown. Figure 35 shows the performance characteristics, and Figure 36 shows the luminance-current efficiency characteristics. In Figure 34, the vertical axis is luminance (c d / m 2 ), with current density (mA / cm²) on the horizontal axis. 2 Figure 35 shows the luminance (cd / m²) on the vertical axis. 2In Figure 36, the horizontal axis shows voltage (V), the vertical axis shows current efficiency (cd / A), and the horizontal axis shows brightness. (cd / m 2 It also indicates 1000 cd / m². 2 Voltage, chromaticity of the light-emitting element in the vicinity, The current efficiency and external quantum efficiency are shown in Table 5.

[0314] [Table 5]

[0315] High luminous efficiency was obtained from both elements, but we will compare light-emitting element 8 and light-emitting element 9. It was found that the light-emitting element 9, which uses BPAFLP in the hole transport layer, has higher current efficiency. Furthermore, comparing the light-emitting element 9 and the light-emitting element 10, the hole injection layer and the hole transport layer It was found that the light-emitting element 10 using BPAFLP had higher current efficiency in both cases.

[0316] Furthermore, regarding light-emitting elements 8 to 10, the initial brightness is set to 1000 cd / cm². 2 as, low Figure 37 shows the results of a continuous lighting test using current drive (vertical axis: 1000 cd / cm²). 2 (This is the relative brightness when set to 100%). From the results in Figure 37, the light-emitting element 8 lasts for 650 hours. Even after 500 hours, it maintained 64% of its initial brightness. It maintained 71% of its brightness. Furthermore, the light-emitting element 10 maintained 7% of its initial brightness even after 500 hours. The brightness remained at 2%. Therefore, BPAFLP (abbreviation) according to one aspect of the present invention is applied. It was found that this method allows for the creation of long-lasting light-emitting elements. [Examples]

[0317] Here, a fluorene derivative, according to one aspect of the present invention, is suitable as a hole transport material. The simulation results suggest this.

[0318] The structural formulas of the organic compounds used in the simulation are shown below.

[0319] [ka]

[0320] First, structural formula (101) (abbreviation: BPAFLP), structural formula (109), structural formula (114 ), (structural formula 151) (abbreviation: BPAFLBi), structural formula (164), and singlet NPB The most stable structure in the state and triplet state was calculated using density functional theory. The quantities used here are The chemical calculation program is Gaussian03. The basis set is for H, C, and N atoms. The model 6-311G(d,p) was used. The functional B3LYP was used.

[0321] Next, using the most stable structures of the singlet and triplet states obtained from the above calculations, the time-dependent Using density functional theory, structural formula (101) (abbreviation: BPAFLP), structural formula (109), Structural formula (114), structural formula (151) (abbreviation: BPAFLBi), structural formula (164), and The excitation energy of NPB was calculated. The same basis and functional as above were used.

[0322] The highest occupied orbital (High Occupancy) of the most stable structure in the singlet state obtained by the above calculations. The energy levels of a pneumatic molecular orbital (HOMO) are The results are shown in Table 6.

[0323] [Table 6]

[0324] From the results in Table 6, the fluorene derivatives mentioned above have a higher HOMO energy level than NPB. It was found to be low. Therefore, when the above fluorene derivative is used as a hole transport material, Compared to NPB, HOMO was found to have superior hole injection capabilities into deeper luminescent layers. Ta.

[0325] Furthermore, the first excitation energy (1) of the most stable structure of the singlet state obtained by TDDFT calculations The results for the repeated terms are shown in Table 7.

[0326] [Table 7]

[0327] From the results in Table 7, when the above fluorene derivative is used as a hole transport material, the ratio with NPB is In contrast, at the boundary between the light-emitting layer and the hole transport layer, it is difficult for singlet excitons to escape to the hole transport layer side. I found out.

[0328] Next, the first excitation energy of the most stable triplet state structure obtained from the TDDFT calculation (triplet The results for item ( ) are shown in Table 8.

[0329] [Table 8]

[0330] From the results in Table 8, when the above fluorene derivatives are used as hole transport materials, they are compared to NPB. In contrast, at the boundary between the light-emitting layer and the hole transport layer, triplet excitons are allowed to escape from the light-emitting layer to the hole transport layer. It was found to be difficult. Also, when the above fluorene derivative is used as a phosphorescent host material... It was found that the guest material was easily excited. [Examples]

[0331] In this Example 9, the fluorene derivative synthesized in Example 1 is 4-phenyl-4'-( Using 9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP) The method for fabricating the light-emitting element and the measurement results of its element characteristics are shown.

[0332] The element structures of the light-emitting element 11 and the comparative light-emitting element 12 in this embodiment 9 are shown in Figure 18. The structure is as shown, and the light-emitting element 11 has a hole injection layer and a hole transport layer, and the full structure of the present invention as described above. It was formed using an olene derivative.

[0333] First, on the glass substrate substrate 1501, indium oxide-tin oxide containing silicon oxide is added. The first electrode 1502 was formed by depositing a film using the sputtering method. The film thickness was 11 The wavelength was set to 0 nm, and the electrode area was set to 2 mm × 2 mm.

[0334] Next, an EL layer 1503 is formed by stacking multiple layers on the first electrode 1502. In this example, the EL layer 1503 is a hole injection layer, the first layer 1511 is a hole transport layer, and The second layer 1512, the third layer 1513 which is a light-emitting layer, and the fourth layer 151 which is an electron transport layer. 4. The structure has a fifth layer 1515, which is an electron injection layer, stacked sequentially.

[0335] The first electrode 1502 is formed such that the surface on which the first electrode 1502 is formed faces downwards. The prepared substrate is fixed to a substrate holder provided inside the vacuum deposition apparatus, 10 -4 Reduced to approximately Pa After pressing, a hole injection material is deposited on the first electrode 1502 to a thickness of 50 nm. Then, a first layer 1511, which is a hole injection layer, was formed. When forming the light-emitting element 11, 4 -phenyl-4'-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: By co-depositing BPAFLP and molybdenum(VI) oxide, a hole injection layer is formed. A first layer 1511 was formed. Its thickness was 50 nm, and it was made of BPAFLP and molybdenum oxide. The ratio of (VI) is such that the weight ratio is 4:2 = (BPAFLP: molybdenum oxide) The deposition rate was adjusted. Also, when forming the comparison light-emitting element 12, ), 4,4',4' '-Tris(carbazole-9-yl)triphenylamine (abbreviation: TCTA) and oxidized mo By co-depositing with ribdenum(VI), a first layer 1511, which is a hole injection layer, is formed. The film thickness was set to 50 nm, and the ratio of TCTA to molybdenum(VI) oxide was determined by weight. The deposition rate was adjusted so that the ratio was 4:2 (TCTA:molybdenum oxide).

[0336] Next, a hole-transporting material is deposited onto the first layer 1511 using a resistive heating deposition method. A film was deposited to a thickness of m, forming a second layer 1512 which is a hole transport layer. When forming the optical element 11, 4-phenyl-4'-(9-phenylfluorene-9- A comparative light-emitting element 12 is formed using yl(triphenylamine) (abbreviated as BPAFLP). In that case, 4,4',4''-tris(carbazole-9-yl)triphenylamine ( Each was formed using (abbreviated as TCTA).

[0337] Next, a third layer, which is an emissive layer, is formed on the second layer using a vapor deposition method with resistance heating. In this example, 9-[4-(4,5-diphenyl-4H-1,2,4-triazole] was used. -3-yl)phenyl]-9H-carbazole (abbreviation: CzTAZI) and bis[2-(4 ',6'-Difluorophenyl)pyridinate-N,C 2’ Iridium(III) picoli By co-depositing with NART (abbreviated as Firpic), a third layer is formed with a thickness of 30 nm. Success. Here, the weight ratio of CzTAZI to Firpic is 1:0.06 = (CzTA The deposition rate was adjusted so that the ratio ZI:FIrpic was obtained.

[0338] Furthermore, 3-(4-biphenylyl) was deposited onto the third layer 1513 using a resistive heating deposition method. )-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (Abbreviation: TAZ01) is 10nm, and bathophenanthroline (Abbreviation: BPhen) is placed on top of it. A film was deposited to a thickness of 20 nm to form a fourth layer 1514, which is an electron transport layer.

[0339] Subsequently, a fifth layer, which is an electron injection layer, and a second electrode are formed, similar to the comparative light-emitting element 1. The light-emitting element 11 and the comparison light-emitting element 12 were fabricated, respectively.

[0340] The light-emitting element 11 and the comparison light-emitting element 12 are made up of the first layer 1511 and the second layer 151 All processes except for number 2 are the same.

[0341] The light-emitting element 11 and the comparative light-emitting element 12 obtained above were placed in a globe box under a nitrogen atmosphere. After sealing the light-emitting elements inside the box to prevent them from being exposed to the atmosphere, these The operating characteristics of the light-emitting element were measured. The measurements were taken in an environment maintained at room temperature (25°C). I went there on a whim.

[0342] Figure 38 shows the current density-luminance characteristics of the light-emitting element 11 and the comparative light-emitting element 12. The pressure-luminance characteristics are shown in Figure 39, and the luminance-current efficiency characteristics are shown in Figure 40. In Figure 38, the vertical axis... Brightness (cd / m²) 2 ), with current density (mA / cm²) on the horizontal axis. 2 ) is shown, and in Figure 39, the vertical axis is luminance. (cd / m 2 In Figure 40, the horizontal axis shows voltage (V), and the vertical axis shows current efficiency (cd / A). The horizontal axis is luminance (cd / m²). 2 It also indicates 1000 cd / m². 2 The electricity of the light-emitting element in the vicinity Pressure, chromaticity, current efficiency, and external quantum efficiency are shown in Table 9.

[0343] [Table 9]

[0344] The fluorene derivative of the present invention, BPAFLP (abbreviated), is used in the first layer 1511 and the second layer The light-emitting element 11 used in layer 1512 has a brightness of 910 cd / m² when the driving voltage is 5.2V. 2 The current value was 0.18mA. TCTA (abbreviation) was used instead of BPAFLP (abbreviation). The comparison light-emitting element 12 used had a brightness of 850 cd / m² when the driving voltage was 5.2V. 2 , current value The current was 0.19mA. From this, it can be concluded that BPA is present in the first layer 1511 and the second layer 1512. The light-emitting element 11 using FLP (abbreviated) has higher current efficiency compared to the comparative light-emitting element 12. It was found that BPAFLP (abbreviated) according to one aspect of the present invention is used in the hole injection layer and By applying it as a hole transport layer, it is possible to obtain a highly efficient light-emitting element. Understood.

[0345] Figure 41 also shows the emission spectra of the light-emitting element 11 and the comparative light-emitting element 12.

[0346] Both the light-emitting element 11 and the comparative light-emitting element 12 are phosphorescent dopant materials Fir Emission spectra originating from PIC (abbreviation) were observed, and from the third layer 1513 and adjacent layers. No light emission was observed. This suggests that neither element had carriers in the third layer 1513. The recombination was successful, and it was possible to induce luminescence with a good carrier balance. Since the light-emitting element 11 shows a higher current efficiency than the comparative light-emitting element 12, BPA FLP (abbreviation) has a better carrier balance (blocking electrons from the third layer 1513). This is because it allows more holes to flow to the third layer 1513, and the triplet excitation energy This suggests that it is also large. (At this time, BPAFLP (abbreviation) according to one aspect of the present invention The LUMO level is almost the same as that of TCTA (abbreviation) (-2.30eV), and the band The gap (Bg) is narrower than that of TCTA (abbreviation) (3.40 eV), therefore this is the origin Because BPAFLP (abbreviation) relating to one aspect of the light is a material with higher hole transport properties, light emission It is believed that the higher efficiency was achieved because carrier recombination occurred efficiently within the layers. (It can be obtained.) [Examples]

[0347] In this example, the fluorene derivative synthesized in Example 1 is 4-phenyl-4'-(9 Using -phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP) The fabrication method of the formed light-emitting element and the measurement results of its element characteristics are shown.

[0348] The element structure of the light-emitting element 13 in this embodiment is as shown in Figure 18, and the hole note The above-mentioned fluorene derivative of the present invention (abbreviated as BPAFLP) is used in the infill layer and the hole transport layer. It was formed by [method]. The structural formula of the organic compound used in this example is shown below.

[0349] First, on the glass substrate substrate 1501, indium oxide-tin oxide containing silicon oxide is added. The first electrode 1502 was formed by depositing a film using the sputtering method. The film thickness was 1 The wavelength was set to 10 nm, and the electrode area was set to 2 mm × 2 mm.

[0350] Next, an EL layer 1503 is formed by stacking multiple layers on the first electrode 1502. In this example, the EL layer 1503 is a hole injection layer, the first layer 1511 is a hole transport layer, and The second layer 1512, the third layer 1513 which is a light-emitting layer, and the fourth layer 151 which is an electron transport layer. 4. The structure has a fifth layer 1515, which is an electron injection layer, stacked sequentially.

[0351] The first electrode 1502 is formed such that the surface on which the first electrode 1502 is formed faces downwards. The prepared substrate is fixed to a substrate holder provided inside the vacuum deposition apparatus, 10 -4 Reduced to approximately Pa After pressing, a hole injection material is deposited on the first electrode 1502 to a thickness of 50 nm. Then, a first layer 1511, which is a hole injection layer, was formed. When forming the light-emitting element 13, 4 -phenyl-4'-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: By co-depositing BPAFLP and molybdenum(VI) oxide, a hole injection layer is formed. A first layer 1511 was formed. Its thickness was 50 nm, and it was made of BPAFLP and molybdenum oxide. The ratio of (VI) is such that the weight ratio is 4:2 = (BPAFLP: molybdenum oxide) I adjusted the arrival rate.

[0352] Next, a hole-transporting material is deposited onto the first layer 1511 using a resistive heating deposition method. A film was deposited to a thickness of m, forming a second layer 1512 which is a hole transport layer. When forming the optical element 13, 4-phenyl-4'-(9-phenylfluorene-9- It was formed using yl)triphenylamine (abbreviated as BPAFLP).

[0353] Next, a third layer, which is an emissive layer, is deposited on the second layer 1512 using a vapor deposition method with resistance heating. It formed 1513. 4-[3-(triphenylene-2-yl)phenyl]dibenzothio Fen (abbreviation: mDBTPTp-II) and Tris(2-phenylpyridinato-N,C) 2’ ) Iridium(III) (abbreviation: Ir(ppy)3), by co-depositing with a third Layer 1513 was formed with a thickness of 40 nm. Here, mDBTPTp-II and Ir(ppy The weight ratio with )3 is 1:0.08 = (mDBTPTp-II:Ir(ppy)3). The deposition rate was adjusted accordingly.

[0354] Furthermore, mDBTPTp-II was deposited onto the third layer 1513 using a resistive heating deposition method. A 10nm layer, on top of which bathophenanthroline (BPhen) is applied to a 20nm film thickness. The film was deposited in this manner to form a fourth layer 1514, which is an electron transport layer.

[0355] Subsequently, a fifth layer, which is an electron injection layer, and a second electrode are formed, similar to the comparative light-emitting element 1. A light-emitting element 13 was fabricated.

[0356] The light-emitting element 13 obtained as described above is subjected to light emission in a glove box under a nitrogen atmosphere. After sealing the element 13 to prevent it from being exposed to the atmosphere, the operating characteristics of the light-emitting element 13 are as follows: Measurements were taken accordingly. The measurements were performed at room temperature (in an atmosphere maintained at 25°C).

[0357] The current density-luminance characteristics of the light-emitting element 13 are shown in Figure 42. The voltage-luminance characteristics are shown in Figure 43. The luminance-current efficiency characteristics are shown in Figure 44. In Figure 42, the vertical axis is luminance (cd / m²). 2 ), The horizontal axis shows current density (mA / cm²). 2 Figure 43 shows the luminance (cd / m²) on the vertical axis. 2 ), horizontal axis The voltage (V) is shown, and in Figure 44, the vertical axis represents current efficiency (cd / A), and the horizontal axis represents luminance (cd / m²). 2 It also indicates 1000 cd / m². 2 The voltage, chromaticity, and current efficiency of the light-emitting element in the vicinity are shown. This is shown in 7.

[0358] [Table 10]

[0359] This embodiment uses the fluorene derivative of the present invention (abbreviated as BPAFLP) to form It was confirmed that the light-emitting element 13 exhibited the characteristics of a light-emitting element and functioned adequately. Based on the reliability test results, even when the light-emitting element is continuously lit, defects in the film, etc., can cause problems. It was found that a highly reliable light-emitting element was obtained without the occurrence of short circuits.

[0360] Furthermore, regarding the light-emitting element 13, the initial brightness is set to 1000 cd / cm². 2 Therefore, by low current drive A continuous lighting test was conducted. From the results, it was found that the light-emitting element 13 maintained its initial brightness even after 1900 hours. It was found to maintain 86% brightness and have a long lifespan. Therefore, according to one aspect of the present invention By applying BPAFLP (abbreviation) as a hole transport layer, a long-life light-emitting element is created. I found out that it is possible to obtain it. [Examples]

[0361] ≪Synthesis Example 3≫ In this embodiment, the full form of the present invention, which is shown as general formula (G1) in Embodiment 1, is shown. Examples of the synthesis of olene derivatives are shown. Specifically, the 4 shown in structural formula (118) of Embodiment 1 -phenyl-3'-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: The synthesis method for mBPAFLP is described below. The structure of mBPAFLP is shown below.

[0362] [ka]

[0363] [Step 1: Synthesis method for 9-(3-bromophenyl)-9-phenylfluorene] In a 200 mL three-necked flask, add 4.2 g (18 mmol) of anhydrous T2-bromoviphenyl. 30 mL of HF solution was added and stirred at -78°C. Then, 1.57 M n-BuLi was added. 11 mL (18 mmol) of hexane solution was added dropwise, and the mixture was stirred for 2.5 hours. Then, 3- Add 40 mL of anhydrous THF solution containing 3.9 g (15 mmol) of bromobenzophenone dropwise, 2 After stirring for a certain amount of time, the mixture was stirred at room temperature for 16 hours.

[0364] After the reaction, a 1N hydrochloric acid solution was added to the mixture and stirred for 1 hour. This mixture was then washed with water. The obtained organic phase was concentrated to obtain a candy-like substance.

[0365] In a 200 mL round-bottom flask, combine this syrupy substance, 20 mL of glacial acetic acid, and 1.0 mL of hydrochloric acid. The mixture was added and heated and stirred at 130°C for 2 hours under a nitrogen atmosphere to allow the reaction to proceed.

[0366] After the reaction, the reaction mixture was added dropwise to 150 mL of ice-cold water. A caramel-like solid was formed. Precipitated. This supernatant was removed by decantation. This caramel-like solid was treated with toluene 1. Dissolve in 00 mL, and while stirring, add saturated sodium bicarbonate solution until no more bubbles are produced. This was added. After washing this organic layer with water, silica gel was added to absorb the moisture. The filtrate obtained by filtering is concentrated, methanol is added, and ultrasonic waves are applied while cooling with ice to produce The solid was filtered off. The target substance was obtained as a white powder in a yield of 4.9 g and 83%. The reaction scheme for the synthesis method is shown below (J-5).

[0367] [ka]

[0368] [Step 2: 4-phenyl-3'-(9-phenylfluoren-9-yl)triphenyl Synthesis method of luamine (abbreviation: mBPAFLP) Add 9-(3-bromophenyl)-9-phenylfluorene to a 200 mL three-necked flask. 2.4g (6.0 mmol), 1.5g (6.0 mmol) of 4-phenyl-diphenylamine ol), sodium tert-butoxide 1.0g (10 mmol), bis(dibenzyl) Add 3.0 mg (0.005 mmol) of zylideneacetone palladium (0) and pour into a flask. The atmosphere inside the container was purged with nitrogen. 25 mL of dehydrated xylene was added to this mixture. After degassing the material while stirring under reduced pressure, tri(tert-butyl)phosphine (10w 0.2 mL (0.1 mmol) of t% hexane solution was added. This mixture was then subjected to a nitrogen atmosphere. The mixture was then heated and stirred at 130°C for 2.5 hours to allow the reaction to proceed.

[0369] After the reaction, add 200 mL of toluene to the reaction mixture, and this suspension is mixed with Florizil and A Lumina, Celite (Wako Pure Chemical Industries, Ltd., catalog number: 531-16855) The solution was filtered. The resulting filtrate was concentrated and subjected to silica gel column chromatography (eluent). Purification was performed using toluene:hexane (1:4). The resulting fraction was concentrated and A After adding cetone and methanol and applying ultrasound, the substance was recrystallized, resulting in a white powder. This was obtained in a yield of 3.2 g and 97%. The reaction scheme of the above synthesis method is shown below (J-6). This will be shown.

[0370] [ka]

[0371] Rf values ​​in silica gel thin-layer chromatography (TLC) (developing solvent: ethyl acetate: Xane (1:10) is the target product, 0.5,1,9-(3-bromophenyl)-9-pheni The levels of fluorene were 0.62 and 4-phenyl-diphenylamine were 0.39.

[0372] The compounds obtained in step 2 above were measured by nuclear magnetic resonance (NMR). The results are as follows: This shows the regular data. Also, 1 The 1H NMR chart is shown in Figure 45. From the measurement results, the above structure mBPAFLP (abbreviated), a fluorene derivative of the present invention represented by formula (118), is obtained. It was discovered that this had happened.

[0373] 1 H NMR (CDCl3,300MHz): δ(ppm)=6.72(d, J=8. 4, 1H), 6.92-7.36(m, 22H), 7.40-7.44(m, 4H), 7 .54-7.57(m, 2H), 7.72-7.75(m, 2H).

[0374] Furthermore, the molecular weight of the compound obtained in step 2 above can be measured using a GC / MS detector (Thermo Measurements were taken using a Fisher ITQ1100 ion trap type GCMS system. This allowed us to detect the main peak with a molecular weight of 561.3 (mode EI+), and to achieve the objective We confirmed that the mBPAFLP (abbreviation) of the substance was obtained.

[0375] Furthermore, various physical properties of the obtained target material, mBPAFLP (abbreviation), were measured as follows. It was decided.

[0376] Absorption spectra (measurement range 200nm~800nm) are measured using a UV-Vis spectrophotometer (Japan) Measurements were taken using a Hikari Corporation V550 model. Figure 46 shows the absorption of toluene solution and thin film. This shows the vector. The horizontal axis represents wavelength (nm), and the vertical axis represents absorption intensity (arbitrary units). Toluene solution The liquid was measured in a quartz cell, and the spectrum was obtained by subtracting the absorption spectra of quartz and toluene. The diagram is shown. Furthermore, a sample of the thin film deposited on a quartz substrate was measured, and the absorption spectrum of the quartz was analyzed. The spectrum with the 'L' subtracted is shown in the diagram. From these spectral diagrams, the absorption peak on the longer wavelength side... These are observed around 310 nm and 325 nm in the case of toluene solution, and 31 nm in the case of thin film. It was found to be present around 2nm and 329nm.

[0377] The emission spectrum was measured using a fluorometer (FS920, Hamamatsu Photonics Ltd.). Figure 47 shows the emission spectra of the toluene solution and the thin film. The horizontal axis is wavelength (nm), and the vertical axis is... The value represents the luminescence intensity (in arbitrary units). The toluene solution was measured in a quartz cell, and the thin film was measured in a quartz cell. Samples deposited on a substrate were measured. From these spectral diagrams, the maximum emission wavelength was determined to be toluene. For solutions, the excitation wavelength is 382 nm (340 nm), and for thin films, it is 393 nm (excitation wavelength). It was found to be 343 nm long.

[0378] The thin film was measured in air using photoelectron spectroscopy (RIKEN Instruments Co., Ltd., AC-2), and the results showed that HOMO The level was -5.73 eV. From the Tauc plot of the thin film absorption spectrum, the absorption edge was It was 3.34 eV. Therefore, the energy gap in the solid state is estimated to be 3.34 eV. This means that the LUMO level is -2.39 eV. From this, mBPAFLP (abbreviation) has a relatively deep HOMO level and a wide band gap (B It was found that it possesses g).

[0379] The redox reaction characteristics were investigated by cyclic voltammetry (CV) measurement. This is an electrochemical analyzer (manufactured by BAS Corporation, model number: ALS Model 600A). (or 600C) was used.

[0380] The oxidation reaction characteristics were observed by changing the potential of the working electrode relative to the reference electrode from 0.38V to 0.69V. After the initial check, measurements were taken by scanning from 0.69V to 0.38V. As a result, the HOMO level was: It was found to be -5.53 [eV]. Furthermore, the oxidation peak remained the same even after 100 cycles. The values ​​were as follows. From this, it can be seen that the repeated oxidation-reduction between the oxidized state and the neutral state is well-suited. It was found to indicate sex.

[0381] The melting point was also measured. The melting point was 211-212°C. [Examples]

[0382] In this example, the fluorene derivative synthesized in Example 1 is 4-phenyl-3'-(9 Using -phenylfluoren-9-yl)triphenylamine (abbreviation: mBPAFLP) The method for fabricating the light-emitting element and the measurement results of its element characteristics are shown.

[0383] The element structure of the light-emitting element in this embodiment is as shown in Figure 18. Light-emitting element 1 4 is a fluorene derivative, which is one embodiment of the present invention described above, in the hole injection layer and the hole transport layer. It is formed using (abbreviated as mBPAFLP).

[0384] First, on the glass substrate substrate 1501, indium oxide-tin oxide containing silicon oxide is added. The first electrode 1502 was formed by depositing a film using the sputtering method. The film thickness was 1 The wavelength was set to 10 nm, and the electrode area was set to 2 mm × 2 mm.

[0385] Next, an EL layer 1503 is formed by stacking multiple layers on the first electrode 1502. In Example 5, the EL layer 1503 is a hole injection layer, and the first layer 1511 is a hole transport layer. A second layer 1512, a third layer 1513 which is an emissive layer, and a fourth layer 15 which is an electron transport layer. 14. It has a structure in which a fifth layer 1515, which is an electron injection layer, is sequentially stacked.

[0386] The first electrode 1502 is formed such that the surface on which the first electrode 1502 is formed faces downwards. The prepared substrate is fixed to a substrate holder provided inside the vacuum deposition apparatus, 10 -4 Reduced to approximately Pa After pressing, a hole injection material is deposited on the first electrode 1502 to a thickness of 50 nm. Then, a first layer 1511, which is a hole injection layer, was formed. When forming the light-emitting element 14, 4 -phenyl-3'-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: By co-depositing mBPAFLP and molybdenum(VI) oxide, a hole injection layer is formed. A first layer 1511 was formed. Its film thickness was 50 nm, and mBPAFLP (abbreviation) and acid The ratio of molybdenum(VI) oxide is 4:2 by weight = (mBPAFLP: molybdenum oxide) The deposition rate was adjusted to achieve the following. Also, when forming the comparative light-emitting element 15, 4,4'-Bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NP) By co-depositing B) and molybdenum(VI) oxide, the first layer 1, which is a hole injection layer, is formed. A 511 film was formed. Its film thickness was 50 nm, and the ratio of NPB to molybdenum(VI) oxide was The deposition rate was adjusted so that the weight ratio was 4:2 = (NPB: molybdenum oxide).

[0387] Next, a hole-transporting material is deposited onto the first layer 1511 using a resistive heating deposition method. A film was deposited to a thickness of m, forming a second layer 1512 which is a hole transport layer. When forming the optical element 14, 4-phenyl-3'-(9-phenylfluorene-9- A comparative light-emitting element 15 is formed using yl(triphenylamine) (abbreviation: mBPAFLP). In that case, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl Each was formed using (abbreviation: NPB).

[0388] Next, a third layer, which is an emissive layer, is deposited on the second layer 1512 using a vapor deposition method with resistance heating. Formed 1513. 9-[4-(10-phenyl-9-antryl)phenyl]-9H -Carbazole (abbreviated as CzPA) and 4-(10-phenyl-9-anthryl)-4'- (9-phenyl-9H-carbazole-3-yl)triphenylamine (abbreviation: PCBA) A third layer 1513 was formed with a thickness of 30 nm by co-depositing PA. The weight ratio of CzPA to PCBAPA is 1:0.075 = (CzPA:PCBAPA) The deposition rate was adjusted to achieve this result.

[0389] Furthermore, using a resistive heating deposition method, tris(8-quinolino) was deposited onto the third layer 1513. Aluminum(III) (abbreviated as Alq) is layered at 10 nm, and then bathophenantho is placed on top of it. A phosphorus (abbreviated as BPhen) film was deposited to a thickness of 20 nm, forming the fourth electron transport layer. This formed layer 1514.

[0390] A lithium fluoride (LiF) film is deposited on the fourth layer 1514 to a thickness of 1 nm. By doing so, a fifth layer 1515, which is an electron injection layer, was formed.

[0391] Finally, using a resistive heating deposition method, aluminum was deposited to a thickness of 200 nm. By forming a film, a second electrode 1504 is formed, and the light-emitting element 14 and the comparison light-emitting element 15 are formed. I made it.

[0392] Furthermore, the light-emitting element 14 and the comparative light-emitting element 15 are located in the first layer 1511 and the second layer 15 All items except for number 12 are produced using the same process.

[0393] The light-emitting element 14 and comparative light-emitting element 15 obtained above were placed in a globe box under a nitrogen atmosphere. After sealing the light-emitting elements inside the box to prevent them from being exposed to the atmosphere, these The operating characteristics of the light-emitting element were measured. The measurements were taken in an environment maintained at room temperature (25°C). I went there on a whim.

[0394] Figure 48 shows the current density-luminance characteristics of the light-emitting element 14 and the comparative light-emitting element 15. The pressure-luminance characteristics are shown in Figure 49, and the luminance-current efficiency characteristics are shown in Figure 50. In Figure 48, the vertical axis... Brightness (cd / m²) 2 ), with current density (mA / cm²) on the horizontal axis. 2 ) is shown, and in Figure 49, the vertical axis is luminance. (cd / m 2 In Figure 50, the horizontal axis shows voltage (V), and the vertical axis shows current efficiency (cd / A). The horizontal axis is luminance (cd / m²). 2 It also shows 1000 cd / cm². 2 Light-emitting elements in the vicinity Voltage, chromaticity, and current efficiency are shown in Table 11.

[0395] [Table 11]

[0396] The light-emitting element 14 has a brightness of 1100 cd / m² when the driving voltage is 3.4V. 2 The current value is 0. It was 72mA. Compared to the comparison light-emitting element 15 which uses an NPB in the second layer 1512, The light-emitting element 14, which uses BPAFLP (abbreviated) in the second layer 1512, has high current efficiency. This was found to be the carrier balance of the light-emitting element 14 compared to the comparison light-emitting element 15. This is likely because it has improved. That is because (compared to NPB) BPAFLP (abbreviation) Because the HOMO level is close to the HOMO level of the host material CzPA (abbreviated) of the emissive layer, This is thought to be because the hole injection ability from the pore transport layer to the light-emitting layer has improved. Furthermore, (PB In comparison, BPAFLP (abbreviated) has a higher LUMO level, which leads to hole transport from the luminescent layer. This is thought to be due to improved electronic blocking properties in the layers. Furthermore, (compared to NPB) Because the band gap (Bg) of BPAFLP (abbreviation) is wide, the third layer 1513 (luminescence) Excitons generated in the layer do not move to the adjacent second layer 1512 (they are not extinguished). This is thought to be because they were trapped.

[0397] Furthermore, the initial brightness of the light-emitting element 14 and the comparative light-emitting element 15 is set to 1000 cd / cm². 2 A continuous lighting test was conducted using low-current drive, with the value set to 100%. From the results, after 280 hours... The light-emitting element 14 maintains a brightness of 80% of its initial brightness, while the comparison light-emitting element 15 maintains a brightness of 72% of its initial brightness. It was found to have a long lifespan. Therefore, the mBPAFLP (abbreviation) of the present invention is suitable It was found that by using this method, long-lasting light-emitting elements can be obtained.

[0398] (Reference example 1) The 4-(10-phenyl-9-antryl)-4'-( used in Examples 3 to 5 above 9-phenyl-9H-carbazole-3-yl)triphenylamine (abbreviation: PCBAP) The synthesis method for A) will be explained in detail.

[0399] [ka]

[0400] 4-(10-phenyl-9-anthryl)-4'-(9-phenyl-9H-carbazole) Synthesis of 3-yl triphenylamine (abbreviation: PCBAPA) Keem is shown below (X-1).

[0401] [ka]

[0402] 9-(4-bromophenyl)-10-phenylanthracene 7.8g (12 mmol) , 4-(9-phenyl-9H-carbazole-3-yl)diphenylamine (abbreviation: PC) BA) 4.8g (12 mmol), sodium tert-butoxide 5.2g (52 mg) The mixture was placed in a 300 mL three-necked flask, and the flask was purged with nitrogen. 60 mL of toluene, 0 mL of tri(tert-butyl)phosphine (10 wt% hexane solution) 0.30 mL was added. This mixture was degassed under reduced pressure while stirring, and after degassing, bis(gibber) 136 mg (0.24 mmol) of palladium(0) (zylideneacetone) was added. The mixture was stirred at 100°C for 3 hours. After stirring, approximately 50 mL of toluene was added to the mixture. Uh, Celite (Wako Pure Chemical Industries, Ltd., catalog number: 531-16855), alumina , through Florizil (Wako Pure Chemical Industries, Ltd., catalog number: 540-00135) The mixture was filtered by suction. The resulting filtrate was concentrated to obtain a yellow solid. This solid was then mixed with toluene / hexane. The material was recrystallized, yielding 6.6 g of the target product, PCBAPA, as a pale yellow solid in 75% yield.

[0403] The resulting pale yellow powdery solid (3.0 g) was purified by sublimation using the train sublimation method. The sublimation purification conditions were: a pressure of 8.7 Pa, and argon gas flow rate of 3.0 mL / min. Next, PCBAPA was heated to 350°C. After sublimation purification, the pale yellow solid PCBAPA was obtained in two stages. 7g was obtained with a recovery rate of 90%.

[0404] The obtained compound was analyzed by nuclear magnetic resonance ( 1 Measurements were taken using 1H NMR. The measurement data is shown below. show.

[0405] 1 H NMR(CDCl3,300MHz):δ=7.09-7.14(m,1H), 7.28-7.72(m,33H),7.88(d,J=8.4Hz,2H),8.19 (d,J=7.2Hz,1H),8.37(d,J=1.5Hz,1H).

[0406] From the measurement results, 4-(10-phenyl-9-antryl)-4'-(9-phenyl-9 H-carbazole-3-yl)triphenylamine (abbreviation: PCBAPA) was obtained. That's what I found out.

[0407] The above 4-(10-phenyl-9-anthryl)-4'-(9-phenyl-9H-cal) By using bazole-3-yl)triphenylamine (abbreviated as PCBAPA), the above The light-emitting elements 1 to 5 shown in the example can be formed.

[0408] (Reference example 2) The 3-phenyl-9-[4-(5-phenyl-1,3] used in Examples 6 and 7 above ,4-Oxadiazole-2-yl)phenyl]-9H-carbazole (abbreviation: CO11 II) The synthesis method will be explained in detail.

[0409] [ka]

[0410] 3-phenyl-9-[4-(5-phenyl-1,3,4-oxadiazole-2-yl The synthesis scheme for phenyl]-9H-carbazole (abbreviation: CO11II) is shown in (Y-1). This will be shown.

[0411] [ka]

[0412] 2-(4-iodophenyl)-5-phenyl-1,3,4-oxadiazole 2.3g (6.6 mmol), 3-phenyl-9H-carbazole 1.6 g (6.6 mmol), 1.4 g (15 mmol) of sodium tert-butoxide in a 100 mL three-necked flask. The mixture was then placed in a flask and the inside of the flask was purged with nitrogen. To this mixture, 30 mL of toluene and tri(ter) Add 0.2 mL of a 10% hexane solution of t-butylphosphine to the flask and then dissolve it in the flask. After degassing the mixture by reducing the pressure with a spiraler, the inside of the flask is purged with nitrogen. This mixture contains bis(dibenzylideneacetone)palladium(0)0.058g(0. Add 10 mmol) and stir under a nitrogen stream at 80°C for 15 hours. After stirring, add to this mixture Toluene was added, and this suspension was washed with saturated sodium carbonate solution and then saturated saline solution. After washing, magnesium sulfate was added to the organic layer to absorb moisture. Then, this mixture was absorbed. The filtrate was obtained by filtration. The obtained filtrate was then processed using Celite (Wako Pure Chemical Industries, Ltd., catalog number...). The filtrate was obtained by suction filtration through (540-16855). The obtained filtrate was concentrated. The compound was purified by silica gel column chromatography. First, toluene is used as the developing solvent, followed by a mixture of toluene and ethyl acetate in a ratio of 4:1. The process was carried out using a medium as the developing solvent. The resulting fraction was concentrated to obtain a solid. Acetone was added and the mixture was washed with ultrasound. The solid was recovered by suction filtration. The recovered solid was recrystallized in a mixed solvent of chloroform and hexane, resulting in a white powder. Solid material was obtained with a yield of 2.0 g and a yield of 64%.

[0413] The obtained white solid (1.1 g) was purified by sublimation using the train sublimation method. The fermentation process was carried out under reduced pressure of 3.0 Pa, with an argon flow rate of 5 mL / min at 240°C for 16 hours. The process was carried out. The yield was 0.98g, and the overall yield was 89%.

[0414] The obtained compounds were measured by nuclear magnetic resonance (1H NMR). The measurement data is shown below. show.

[0415] 1 H NMR(CDCl3,300MHz):δ=7.30-7.76(m,13H) , 7.79(d,J=8.3Hz,2H), 8.14-8.24(m,3H), 8.35 (sd,J=1.5Hz,1H), 8.39(d,J=8.8Hz,2H).

[0416] From the measurement results, 3-phenyl-9-[4-(5-phenyl-1,3,4-oxadiazo The compound 2-yl phenyl]-9H-carbazole (abbreviated as CO11II) was obtained. You can understand that.

[0417] The above-mentioned 3-phenyl-9-[4-(5-phenyl-1,3,4-oxadiazole-2 By using -yl)phenyl]-9H-carbazole (abbreviation: CO11II), the above The light-emitting elements 6 to 10 shown in the example can be formed.

[0418] (Reference example 3) The 4-phenyl-4'-(9-phenyl-9H-carbazole-3 used in Example 7 above Please explain in detail the synthesis method of -yl)triphenylamine (abbreviation: PCBA1BP). do.

[0419] [ka]

[0420] 4-Phenyl-4'-(9-phenyl-9H-carbazole-3-yl)triphenyl The synthesis scheme for the amine (abbreviation: PCBA1BP) is shown in (Z-1).

[0421] [ka]

[0422] 4-(9-phenyl-9H-carbazole-3-yl)diphenylamine 2.0g (4 0.9 mmol), 4-bromoviphenyl 1.1 g (4.9 mmol), sodium te Place 2.0 g (20 mmol) of rt-butoxide into a 100 mL three-necked flask, and then... The inside was purged with nitrogen. To this mixture, 50 mL of toluene and tri(tert-butyl)phosphorus were added. 0.30 mL of phenyl (10 wt% hexane solution) was added.

[0423] This mixture is degassed while stirring under reduced pressure, and after degassing, bis(dibenzylideneacetone) 0.10 g of palladium(0) was added. Next, this mixture was heated and stirred at 80°C for 5 hours. The reaction was carried out. After the reaction, toluene was added to the reaction mixture, and this suspension was used to make a ceramic solution. Ito (Wako Pure Chemical Industries, Ltd., catalog number: 531-16855), alumina, fluorine Suction filtration via Zeal (Wako Pure Chemical Industries, Ltd., catalog number: 540-00135) Then, a filtrate was obtained. The obtained filtrate was washed with saturated sodium carbonate solution and then saturated saline solution. Magnesium sulfate was added to the organic layer to adsorb moisture. After drying, the mixture was filtered by suction. Then, magnesium sulfate was removed to obtain the filtrate.

[0424] The obtained filtrate was concentrated and purified by silica gel column chromatography. In Ricagel column chromatography, the first step is to separate the toluene and hexane in a 1:9 mixed solvent. It is used as a solvent, and then a mixed solvent of toluene:hexane = 3:7 is used as the developing solvent. This was done by concentrating the resulting fraction to obtain a solid, which was then mixed with chloroform and hexane. When recrystallized with a mixed solvent, the yield of white powdery solid was 2.3 g, and the yield was 84%. there were.

[0425] The obtained white solid (1.2 g) was purified by sublimation using the train sublimation method. The fermentation process was carried out under reduced pressure of 7.0 Pa, with an argon flow rate of 3 mL / min at 280°C for 20 hours. The experiment was conducted over time. The yield was 1.1g, and the yield rate was 89%.

[0426] The obtained compound was analyzed by nuclear magnetic resonance ( 1 Measurements were taken using 1H NMR. The measurement data is shown below. show.

[0427] 1 H NMR(DMSO-d6,300MHz):δ(ppm)=7.05-7.20 (m,7H),7.28-7.78(m,21H),8.34(d,J=7.8Hz,1 H), 8.57 (s, 1H)

[0428] From the measurement results, 4-phenyl-4'-(9-phenyl-9H-carbazole-3-yl )It can be seen that triphenylamine (abbreviated as PCBA1BP) was obtained.

[0429] The above-mentioned 4-phenyl-4'-(9-phenyl-9H-carbazole-3-yl) truffle By using phenylamine (abbreviated as PCBA1BP), the light-emitting element 8 shown in the previous example can be generated. ~A light-emitting element 10 can be formed.

[0430] (Reference example 4) As explained in Reference Example 3, 4-phenyl-4'-(9-phenyl-9H-carbazole-3- This document specifically describes another method for synthesizing yl(triphenylamine) (abbreviated as PCBA1BP). This synthesis method is preferable because it yields a higher purity of the target product in good yield, is simple, and therefore preferable.

[0431] [ka]

[0432] [Step 1: Synthesis of 3-(4-bromophenyl)-9-phenyl-9H-carbazole] Law] The synthesis scheme for 3-(4-bromophenyl)-9-phenyl-9H-carbazole is shown in (Z As shown in -2).

[0433] [ka]

[0434] In a 300 mL three-necked flask, 14 g (50 mmol) of 4-bromoiodobenzene, 9 -Phenyl-9H-carbazole-3-boronic acid 14g (50 mmol), paradipropyl acetate Mu(II) 110 mg (0.5 mmol), Tri(o-tril)phosphine 300 mg ( 1.0 mmol) toluene 50 mL, ethanol 10 mL, 2 mol / L potassium carbonate After degassing the 25 mL aqueous solution mixture under reduced pressure while stirring, it was then stored under a nitrogen atmosphere at 80°C. The mixture was heated and stirred for 6 hours to allow it to react.

[0435] After the reaction, add 200 mL of toluene to the reaction mixture, and this suspension is mixed with Florizil (Japanese Wako Pure Chemical Industries, Ltd. (Catalog number: 540-00135), Celite (Wako Pure Chemical Industries, Ltd.) The filtrate was filtered through (a chemical company, catalog number: 531-16855). The resulting filtrate was washed with water. The suspension was purified, and magnesium sulfate was added to adsorb the water. This suspension was filtered to obtain the filtrate. The obtained filtrate was concentrated and purified by silica gel column chromatography. At that time, a mixed solvent of toluene and hexane is used as the developing solvent for chromatography (toluene A mixture of hexane (1:4) was used. The resulting fraction was concentrated, and hexane was added to produce an ultrasonic sound. After applying waves and then recrystallizing, the target substance was obtained as a white powder in a yield of 15 g and a yield of 75%. .

[0436] Rf values ​​in silica gel thin-layer chromatography (TLC) (developing solvent: ethyl acetate: For xane (1:10), the target substance was 0.32 and 4-bromoiodobenzene was 0.74. .

[0437] Additionally, the by-product, 1,4-bis(9-phenyl-9H-carbazole-3-yl) The Rf value of hexane (developing solvent ethyl acetate:hexane = 1:10) was 0.23, but the reaction Only faint spots were observed on the TLC in the reaction suspension. This indicates that the raw materials and The iodine portion of 4-bromoiodobenzene, a dihalide used in this process, is bromo Because it is more reactive than the other part, the boron compound, 9-phenyl It was found to have reacted with -9H-carbazole-3-boronic acid (i.e., dihalogenation). We were able to react the substance with a boron compound in an almost 1:1 ratio. Furthermore, we were able to determine the Rf value of the target product and the byproducts. Since the Rf value is sufficiently far from that of the product, in the column purification described above, the target product and by-products are separated. It was possible to easily separate the object from the object.

[0438] The compounds obtained in step 1 above were measured by nuclear magnetic resonance (NMR). This shows the regular data.

[0439] 1 H NMR(CDCl3,300MHz):δ(ppm)=7.24-7.32(m ,1H), 7.40-7.64(m,13H), 8.17(d,J=7.2,1H), 8 .29 (s, 1H).

[0440] From the measurement results, the target substance was identified as 3-(4-bromophenyl)-9-phenyl-9H-cal We confirmed that basol was obtained.

[0441] The molecular weight of the above compound was determined using a GC-MS detector (Thermo Fisher, ITQ1). Measured using a 100-ion trap type GCMS system. Molecular weight 397.13 (molecular weight). The device detects a peak mainly consisting of EI+, and from the measurement results, it identifies the target substance as 3-(4- It was confirmed that romofenyl)-9-phenyl-9H-carbazole was obtained.

[0442] Furthermore, this GC-MS detection also detects the by-product 1,4-bis(9-phenyl-9H- No peaks originating from ruvacol-3-yl)benzene (molecular weight 560.2) were detected. Therefore, by performing the reaction in Step 1, the target product can be obtained in very high yield, simply, and with high purity. You can see what was gained.

[0443] [Step 2: 4-phenyl-4'-(9-phenyl-9H-carbazole-3-yl) Synthesis method of triphenylamine (abbreviation: PCBA1BP) 4-phenyl-4'-(9-phenyl-9H-carbazole-3-yl)triphenyl The synthesis scheme for min (abbreviated as PCBA1BP) is shown in (Z-3).

[0444] [ka] 4-phenyl-diphenylamine and 3-(4-bromophenyl)-9-phenyl-9 H-carbazole is used with a palladium catalyst, a palladium catalyst ligand, and a base. The mixture was heated and stirred in an organic solvent to allow the reaction to proceed.

[0445] After the reaction, the reaction mixture was purified to obtain the target product as a white powder.

[0446] The obtained compound was analyzed by nuclear magnetic resonance ( 1 The measurement was performed using 1H NMR. Based on the measurement results, for reference... Similar to Example 3, the target product is 4-phenyl-4'-(9-phenyl-9H-carbazole-3) It was found that -yl)triphenylamine (abbreviated as PCBA1BP) was obtained.

[0447] Based on the above, the synthesis method shown in Reference Example 4 allows for the simple and efficient acquisition of the target product in high purity with good yield. It was discovered that... [Explanation of symbols]

[0448] 101 circuit board 102 First electrode 103 EL layer 104 Second electrode 111 layers 112 layers 113 layers 114 layers 115 layers 301 Electrode 302 Electrode 303 EL layer 304 EL layer 305 Charge generation layer 401 Source-side drive circuit 402 pixel section 403 Gate-side drive circuit 404 Sealing substrate 405 sealant 407 Space 408 Wiring 409 FPC (Flexible Printed Circuit) 410 element substrate 411 Switching TFT 412 Current-controlled TFT 413 First electrode 414 Insulators 416 EL layer 417 Second electrode 418 Light-emitting element 423 N-channel TFT 424 P-channel TFT 501 circuit board 502 First electrode 503 Second electrode 504 EL layer 505 Insulating layer 506 Partition layer 511 First light-emitting unit 512 Second light-emitting unit 513 Charge generation layer 521 First electrode 522 Second electrode 611 cabinet 612 Support stand 613 Display section 614 Speaker section 615 Video Input Terminals 621 Main Unit 622 cabinets 623 Display section 624 keyboard 625 External connection port 626 Pointing Devices 631 Main Unit 632 cabinets 633 Display section 634 Voice Input Section 635 Audio output section 636 Operation Keys 637 External connection port 638 Antenna 641 Main Unit 642 Display section 643 cabinets 644 External connection ports 645 Remote control receiver 646 Image receiving section 647 Battery 648 Voice input section 649 Operation Keys 650 Eyepiece 701 cabinet 702 Liquid Crystal Layer 703 Backlight 704 cabinet 705 Driver IC 706 terminal 801 cabinet 802 light source 901 Lighting device 902 Television equipment 913 layers 1501 circuit board 1502 First electrode 1503 EL layer 1504 Second electrode 1511 layers 1512 layers 1513 layers 1514 layers 1515 layers

Claims

1. Having an anode, a cathode, a first layer, and a second layer, The first layer is located between the anode and the second layer. The second layer is located between the first layer and the cathode. The first layer has a monoamine compound represented by general formula (G1), The second layer is a light-emitting element having a light-emitting material. 【Chemistry 1】 (In the formula, R1 to R8 each independently represent a hydrogen atom. α1 and α2 each independently represent a substituted or unsubstituted phenylene group. Ar1 represents an aryl group having 6 to 13 carbon atoms that forms a ring. Ar2 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar3 represents any of an alkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. If the aryl group having 6 to 12 carbon atoms has a substituent, the substituent is any of an alkyl group, a phenyl group, a biphenyl group, and a naphthyl group. m and n are each independently 0 or 1. J is 0, and α4 is a substituted or unsubstituted phenylene group. k is 1, and α3 (This refers to a substituted or unsubstituted phenylene group, except in the case of a paraphenylene group.)

2. Having an anode, a cathode, a first layer, and a second layer, The first layer is located between the anode and the second layer. The second layer is located between the first layer and the cathode. The first layer has a monoamine compound represented by general formula (G1), The second layer is a light-emitting element having a light-emitting material. 【Chemistry 2】 (In the formula, R1 to R8 each independently represent a hydrogen atom. α1 and α2 each independently represent a substituted or unsubstituted phenylene group. Ar1 represents an aryl group having 6 to 13 carbon atoms that forms a ring. Ar2 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar3 represents any of an alkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. If the aryl group having 6 to 12 carbon atoms has a substituent, the substituent is any of an alkyl group, a phenyl group, a biphenyl group, and a naphthyl group. m and n are each independently 0 or 1. J is 0, and α4 is a substituted or unsubstituted phenylene group. k is 1, and α3 α is a substituted or unsubstituted phenylene group (except in the case of a paraphenylene group). If α3 has a substituent, the substituent is one of an alkyl group, a phenyl group, a biphenyl group, or a naphthyl group.

3. Having an anode, a cathode, a first layer, and a second layer, The first layer is located between the anode and the second layer. The second layer is located between the first layer and the cathode. The first layer has a monoamine compound represented by general formula (G1), The second layer is a light-emitting element having a light-emitting material. 【Transformation 3】 (In the formula, R1 to R8 each independently represent a hydrogen atom. α1 and α2 each independently represent a substituted or unsubstituted phenylene group. Ar1 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar2 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar3 represents any of a C1 to C6 alkyl group and a substituted or unsubstituted C6 to C12 aryl group. If the C6 to C12 aryl group has a substituent, the substituent is any of an alkyl group, a phenyl group, a biphenyl group, and a naphthyl group. m and n are each independently 0 or 1. J is 0, and α4 is a substituted or unsubstituted phenylene group. k is 1, and α3 is a substituted or unsubstituted phenylene group (except when it is a paraphenylene group).

4. Having an anode, a cathode, a first layer, and a second layer, The first layer is located between the anode and the second layer. The second layer is located between the first layer and the cathode. The first layer has a monoamine compound represented by general formula (G1), The second layer is a light-emitting element having a light-emitting material. 【Chemistry 4】 (In the formula, R1 to R8 each independently represent a hydrogen atom. α1 and α2 each independently represent a substituted or unsubstituted phenylene group. Ar1 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar2 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar3 represents any of a C1 to C6 alkyl group and a substituted or unsubstituted C6 to C12 aryl group. If the C6 to C12 aryl group has a substituent, the substituent is any of an alkyl group, a phenyl group, a biphenyl group, and a naphthyl group. m and n are each independently 0 or 1. J is 0, and α4 α is a substituted or unsubstituted phenylene group. k is 1, and α3 is a substituted or unsubstituted phenylene group (except when it is a paraphenylene group). If α3 has a substituent, the substituent is one of an alkyl group, a phenyl group, a biphenyl group, or a naphthyl group.

5. Having an anode, a cathode, a first layer, and a second layer, The first layer is located between the anode and the second layer. The second layer is located between the first layer and the cathode. The first layer has a monoamine compound represented by general formula (G1), The second layer is a light-emitting element having a light-emitting material. 【Transformation 5】 (In the formula, R1 to R8 each independently represent a hydrogen atom. α1 and α2 each independently represent a substituted or unsubstituted phenylene group. Ar1 represents an aryl group having 6 to 13 carbon atoms that forms a ring. Ar2 represents one of a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted spirofluorenyl group. Ar3 represents one of an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. If the aryl group having 6 to 12 carbon atoms has a substituent, the substituent is one of an alkyl group, a phenyl group, a biphenyl group, or a naphthyl group. m and n are each independently 0 or 1. J is 0, and α4 is a substituted or unsubstituted phenylene group. k is 1, and α3 is a substituted or unsubstituted phenylene group (except when it is a paraphenylene group).)

6. Having an anode, a cathode, a first layer, and a second layer, The first layer is located between the anode and the second layer. The second layer is located between the first layer and the cathode. The first layer has a monoamine compound represented by general formula (G1), The second layer is a light-emitting element having a light-emitting material. 【Transformation 6】 (In the formula, R1 to R8 each independently represent a hydrogen atom. α1 and α2 each independently represent a substituted or unsubstituted phenylene group. Ar1 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar2 represents any of a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar3 represents any of a C1 to C6 alkyl group and a substituted or unsubstituted C6 to C12 aryl group. If the C6 to C12 aryl group has a substituent, the substituent is any of an alkyl group, a phenyl group, a biphenyl group, and a naphthyl group. m and n are each independently 0 or 1. J is 0, and α4 α is a substituted or unsubstituted phenylene group. k is 1, and α3 is a substituted or unsubstituted phenylene group (except when it is a paraphenylene group). If α3 has a substituent, the substituent is one of an alkyl group, a phenyl group, a biphenyl group, or a naphthyl group.

7. Having an anode, a cathode, a first layer, and a second layer, The first layer is located between the anode and the second layer. The second layer is located between the first layer and the cathode. The first layer has a monoamine compound represented by general formula (G1), The second layer is a light-emitting element having a phosphorescent material. 【Transformation 7】 (In the formula, R1 to R8 each independently represent a hydrogen atom. α1 and α2 each independently represent a substituted or unsubstituted phenylene group. Ar1 represents an aryl group having 6 to 13 carbon atoms that forms a ring. Ar2 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar3 represents any of an alkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. If the aryl group having 6 to 12 carbon atoms has a substituent, the substituent is any of an alkyl group, a phenyl group, a biphenyl group, and a naphthyl group. m and n are each independently 0 or 1. J is 0, and α4 is a substituted or unsubstituted phenylene group. k is 1, and α3 (This refers to a substituted or unsubstituted phenylene group, except in the case of a paraphenylene group.)

8. Having an anode, a cathode, a first layer, and a second layer, The first layer is located between the anode and the second layer. The second layer is located between the first layer and the cathode. The first layer has a monoamine compound represented by general formula (G1), The second layer is a light-emitting element having a phosphorescent material. 【Transformation 8】 (In the formula, R1 to R8 each independently represent a hydrogen atom. α1 and α2 each independently represent a substituted or unsubstituted phenylene group. Ar1 represents an aryl group having 6 to 13 carbon atoms that forms a ring. Ar2 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar3 represents any of an alkyl group having 1 to 6 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. If the aryl group having 6 to 12 carbon atoms has a substituent, the substituent is any of an alkyl group, a phenyl group, a biphenyl group, and a naphthyl group. m and n are each independently 0 or 1. J is 0, and α4 is a substituted or unsubstituted phenylene group. k is 1, and α3 α is a substituted or unsubstituted phenylene group (except in the case of a paraphenylene group). If α3 has a substituent, the substituent is one of an alkyl group, a phenyl group, a biphenyl group, or a naphthyl group.

9. Having an anode, a cathode, a first layer, and a second layer, The first layer is located between the anode and the second layer. The second layer is located between the first layer and the cathode. The first layer has a monoamine compound represented by general formula (G1), The second layer is a light-emitting element having a phosphorescent material. 【Chemistry 9】 (In the formula, R1 to R8 each independently represent a hydrogen atom. α1 and α2 each independently represent a substituted or unsubstituted phenylene group. Ar1 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar2 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar3 represents any of a C1 to C6 alkyl group and a substituted or unsubstituted C6 to C12 aryl group. If the C6 to C12 aryl group has a substituent, the substituent is any of an alkyl group, a phenyl group, a biphenyl group, and a naphthyl group. m and n are each independently 0 or 1. J is 0, and α4 is a substituted or unsubstituted phenylene group. k is 1, and α3 is a substituted or unsubstituted phenylene group (except when it is a paraphenylene group).

10. Having an anode, a cathode, a first layer, and a second layer, The first layer is located between the anode and the second layer. The second layer is located between the first layer and the cathode. The first layer has a monoamine compound represented by general formula (G1), The second layer is a light-emitting element having a phosphorescent material. 【Chemistry 10】 (In the formula, R1 to R8 each independently represent a hydrogen atom. α1 and α2 each independently represent a substituted or unsubstituted phenylene group. Ar1 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar2 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar3 represents any of a C1 to C6 alkyl group and a substituted or unsubstituted C6 to C12 aryl group. If the C6 to C12 aryl group has a substituent, the substituent is any of an alkyl group, a phenyl group, a biphenyl group, and a naphthyl group. m and n are each independently 0 or 1. J is 0, and α4 α is a substituted or unsubstituted phenylene group. k is 1, and α3 is a substituted or unsubstituted phenylene group (except when it is a paraphenylene group). If α3 has a substituent, the substituent is one of an alkyl group, a phenyl group, a biphenyl group, or a naphthyl group.

11. Having an anode, a cathode, a first layer, and a second layer, The first layer is located between the anode and the second layer. The second layer is located between the first layer and the cathode. The first layer has a monoamine compound represented by general formula (G1), The second layer is a light-emitting element having a phosphorescent material. 【Chemistry 11】 (In the formula, R1 to R8 each independently represent a hydrogen atom. α1 and α2 each independently represent a substituted or unsubstituted phenylene group. Ar1 represents an aryl group having 6 to 13 carbon atoms that forms a ring. Ar2 represents one of a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted spirofluorenyl group. Ar3 represents one of an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. If the aryl group having 6 to 12 carbon atoms has a substituent, the substituent is one of an alkyl group, a phenyl group, a biphenyl group, or a naphthyl group. m and n are each independently 0 or 1. J is 0, and α4 is a substituted or unsubstituted phenylene group. k is 1, and α3 is a substituted or unsubstituted phenylene group (except when it is a paraphenylene group).)

12. Having an anode, a cathode, a first layer, and a second layer, The first layer is located between the anode and the second layer. The second layer is located between the first layer and the cathode. The first layer has a monoamine compound represented by general formula (G1), The second layer is a light-emitting element having a phosphorescent material. 【Chemistry 12】 (In the formula, R1 to R8 each independently represent a hydrogen atom. α1 and α2 each independently represent a substituted or unsubstituted phenylene group. Ar1 represents any of a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar2 represents any of a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted spirofluorenyl group. Ar3 represents any of a C1 to C6 alkyl group and a substituted or unsubstituted C6 to C12 aryl group. If the C6 to C12 aryl group has a substituent, the substituent is any of an alkyl group, a phenyl group, a biphenyl group, and a naphthyl group. m and n are each independently 0 or 1. J is 0, and α4 α is a substituted or unsubstituted phenylene group. k is 1, and α3 is a substituted or unsubstituted phenylene group (except when it is a paraphenylene group). If α3 has a substituent, the substituent is one of an alkyl group, a phenyl group, a biphenyl group, or a naphthyl group.

13. In any one of Claims 1 to 12, Ar3 is a light-emitting element in which the substituent is one of those represented by the following formulas (Ar3-6) to (Ar3-8). 【Chemistry 13】

14. In any one of Claims 1 to 13, The first layer is a light-emitting element adjacent to the second layer.

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